Preparation of Si-H containing iodosilanes via halide exchange reaction

ABSTRACT

Methods of synthesizing Si—H containing iodosilanes, such as diiodosilane or pentaiododisilane, using a halide exchange reaction are disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. patent application Ser.No. 15/836,518, filed Dec. 8, 2017, which is a continuation-in-part ofPCT Patent Application Serial No. PCT/US2017/033620 filed May 19, 2017,which claims the benefit of U.S. Provisional Application Ser. No.62/338,882 filed May 19, 2016, and to Taiwan Patent Application No.106139942 filed Nov. 17, 2017, all herein incorporated by reference intheir entireties for all purposes.

TECHNICAL FIELD TO WHICH THE INVENTION RELATES

Methods of synthesizing Si—H containing iodosilanes, such asdiiodosilane or pentaiododisilane, using a halide exchange reaction aredisclosed.

BACKGROUND OF THE INVENTION

Halosilane chemicals find many uses in industry. In particular,iodosilane precursors, such as diiodosilane (SiH₂I₂), are used todeposit a variety of silicon containing films for use in semiconductormanufacturing processes.

Emeléus et al., disclose synthesis of diiodosilane (SiH₂I₂) by reactionof Silane (SiH₄), Hydrogen Iodide (HI), and aluminum iodide (AlI₃).Derivatives of monosilane. Part II. The lodo compounds: Emeleus, H. J.;Maddock, A. G.; Reid, C., J. Chem. Soc. 1941, 353-358). The reactionproduces the desired SiH₂I₂ reaction product along with lodosilane(SiH₃I), Triiodosilane (SiHI₃), and tetraiodosilane (SiI₄). Id. at p.354.

Keinan et al. disclose the reaction of iodine and phenylsilane in a 1:1molar ratio in the presence of traces of ethyl acetate at −20° C.produces 1 mol of SiH₂I₂ and 1 mol of benzene. J. Org. Chem., Vol. 52,No. 22, 1987, pp. 4846-4851. Although selective for SiH₂I₂ over theother possible iodosilanes (i.e., SiH₃I, SiHI₃, and SiI₄), this methodproduces the known human carcinogen benzene, which makes commercialimplementation difficult. Despite this drawback, it remains thepreferred synthetic approach to producing Diiodosilane.

Impurities from these synthesis processes, such as hydrogen iodideand/or iodine, may decompose the resulting iodosilane product. Currentindustrial practice is to stabilize these products using antimony,silver, or copper powder/pellet additives as taught in Eaborn,‘Organosilicon Compounds. Part II. ‘A Conversion Series forOrganosilicon Halides, Pseudohalides, and Sulphides’, 1950, J. Chem.Soc., 3077-3089 and Beilstein 4, IV, 4009. Although the addition ofcopper may stabilize the product, it also may introduce impurities (Cu)which may adversely affect the electrical properties of the depositedfilms.

The so-called Finkelstein reaction is an S_(N)2 reaction (SubstitutionNucleophilic Bimolecular reaction) that involves the exchange of onehalogen atom for another. Halide exchange is an equilibrium reaction,but the reaction can be driven to completion by exploiting thedifferential solubility of halide salts, or by using a large excess ofthe halide salt. Smith et al., (2007), Advanced Organic Chemistry:Reactions, Mechanisms, and Structure (6th ed.), New York:Wiley-Interscience.

For example, the preparation of trimethylsilyl iodide (TMS-I) viareactions of trimethylsilyl chloride and lithium iodide in chloroform orsodium iodide in acetonitrile has been reported (Eq. 4). Handbook ofReagents for Organic Synthesis, Reagents for Silicon-Mediated OrganicSynthesis, Iodotrimethylsilane, Wiley 2011, p. 325

While Si—Cl is reactive to iodine exchange by this route, R groups likealkyl or aryl groups are not. On the other hand, Si—H bonds are found ingeneral to be more reactive than the Si—Cl bond. Chemistry andTechnology of Silicones, Academic Press, 1968, p. 50. As a result, oneof ordinary skill in the art would expect exchange of both the H and Clatoms of any Si—H containing halosilane in the Finkelstein reaction.

A need remains for commercially viable synthesis and supply of stableSi—H containing iodosilanes, such as diiodosilane, suitable for use inthe semiconductor industry.

BRIEF SUMMARY

Methods of synthesizing Si—H containing iodosilanes are disclosed. TheSi—H containing iodosilanes have the formulaSi_(w)H_(x)R_(y)I_(z)  (1)N(SiH_(a)R_(b)I_(c))₃  (2) or(SiH_(m)R_(n)I_(o))₂—CH₂  (3)wherein w is 1 to 3, x+y+z=2w+2, x is 1 to 2w+1, y is 0 to 2w+1, z is 1to 2w+1, each a is independently 0 to 3, each b is independently 0 to 3,each c is independently 0 to 3, a+b+c=3 provided that at least one a andat least one c is 1, each m is independently 0 to 3, each n isindependently 0 to 3, each o is independently 0 to 3, m+n+o=3 providedthat at least one m and at least one o is 1, and each R is independentlya C1 to C12 hydrocarbyl group, Cl, Br, or a ER′₃ group, wherein each Eis independently Si or Ge and each R′ is independently H or a C1 to C12hydrocarbyl group. A halosilane reactant having the formulaSi_(w)H_(x)R_(y)X_(z), N(SiH_(a)R_(b)X_(c))₃, or(SiH_(m)R_(n)X_(o))₂—CH₂, wherein X is Cl or Br, and w, x, y, z, a, b,c, m, n, and o are as defined above, is reacted with an alkali metalhalide reactant having the formula MI, wherein M=Li, Na, K, Rb, or Cs,to produce a mixture of Si_(w)H_(x)R_(y)I_(z), N(SiH_(a)R_(b)I_(c))₃ or(SiH_(m)R_(n)I_(o))₂—CH₂ and MX. The Si—H containing iodosilane havingthe formula Si_(w)H_(x)R_(y)I_(z), N(SiH_(a)R_(b)I_(c))₃ or(SiH_(m)R_(n)I_(o))₂—CH₂ is isolated from the mixture. Alternatively,the halosilane reactant is contacted with the alkali metal halidereactant to produce the combination of MX and Si_(w)H_(x)I_(z),N(SiH_(a)R_(b)I_(c))₃ or (SiH_(m)R_(n)I_(o))₂—CH₂. The Si—H containingiodosilane having the formula Si_(w)H_(x)I_(z), N(SiH_(a)R_(b)I_(c))₃ or(SiH_(m)R_(n)I_(o))₂—CH₂ is isolated from the mixture. Either of thedisclosed methods may have one or more of the following aspects:

-   -   R is not Cl or Br;    -   R is a C1 to C12 hydrocarbyl group;    -   R is a C1 to C4 hydrocarbyl group;    -   R is a ER′₃ group;    -   M=Li;    -   y=0;    -   z=2 to 2w+1;    -   adding a solvent to the reacting step;    -   the solvent being the Si—H containing iodosilane;    -   the solvent being an alkane;    -   the solvent being propane, butane, pentane, hexane, heptanes,        chloromethane, dichloromethane, chloroform, carbon        tetrachloride, methylene chloride, acetonitrile, and        combinations thereof;    -   the solvent being pentane;    -   the isolating step comprising filtering the mixture to separate        MX from the Si—H containing iodosilane having the formula        Si_(w)H_(x)R_(y)I_(z);    -   the halosilane reactant being SiH₂Cl₂;    -   the halosilane reactant being Si₂HCl₅;    -   the halosilane reactant being (SiH₃)₂N(SiH₂Cl);    -   the alkali metal halide reactant being LiI;    -   the Si—H containing iodosilanes have the formula        Si_(w)H_(x)R_(y)I_(z) (1);    -   the Si—H containing iodosilane having the formula        SiH_(x)I_(4-x), wherein x=1 to 3;    -   the Si—H containing iodosilane being SiHI₃;    -   the Si—H containing iodosilane being SiH₂I₂;    -   the Si—H containing iodosilane being SiH₃I;    -   the Si—H containing iodosilane having the formula        SiH_(x)R_(y)I_(4-x-y), wherein x=1 to 2, y=1 to 2, x+y is less        than or equal to 3, and each R is independently a C1 to C12        hydrocarbyl group, Cl, Br, or a ER′₃ group, wherein each E is        independently Si or Ge and each R′ is independently H or a C1 to        C12 hydrocarbyl group;    -   the Si—H containing iodosilane being MeSiHI₂;    -   the Si—H containing iodosilane being MeSiH₂I;    -   the Si—H containing iodosilane being Me₂SiHI;    -   the Si—H containing iodosilane being EtSiHI₂;    -   the Si—H containing iodosilane being EtSiH₂I;    -   the Si—H containing iodosilane being Et₂SiHI;    -   the Si—H containing iodosilane being ClSiHI₂;    -   the Si—H containing iodosilane being ClSiH₂I;    -   the Si—H containing iodosilane being Cl₂SiHI;    -   the Si—H containing iodosilane being BrSiHI₂;    -   the Si—H containing iodosilane being BrSiH₂I;    -   the Si—H containing iodosilane being BrI₂SiHI;    -   the Si—H containing iodosilane being H₃SiSiHI₂;    -   the Si—H containing iodosilane being H₃SiSiH₂I;    -   the Si—H containing iodosilane being (H₃Si)₂SiHI;    -   the Si—H containing iodosilane being H₃GeSiHI₂;    -   the Si—H containing iodosilane being H₃GeSiH₂I;    -   the Si—H containing iodosilane being (H₃Ge)₂SiHI;    -   the Si—H containing iodosilane being Me₃SiSiHI₂;    -   the Si—H containing iodosilane being Me₃SiSiH₂I;    -   the Si—H containing iodosilane being (Me₃Si)₂SiHI;    -   the Si—H containing iodosilane being Me₃GeSiHI₂;    -   the Si—H containing iodosilane being Me₃GeSiH₂I;    -   the Si—H containing iodosilane being (Me₃Ge)₂SiHI;    -   the Si—H containing iodosilane being Me₂HSiSiHI₂;    -   the Si—H containing iodosilane being Me₂HSiSiH₂I;    -   the Si—H containing iodosilane being (Me₂HSi)₂SiHI;    -   the Si—H containing iodosilane being Me₂HGeSiHI₂;    -   the Si—H containing iodosilane being Me₂HGeSiH₂I;    -   the Si—H containing iodosilane being (Me₂HGe)₂SiHI;    -   the Si—H containing iodosilane having the formula        Si₂H_(x)I_(6-x), wherein x=1-5;    -   the Si—H containing iodosilane being Si₂HI₅;    -   the Si—H containing iodosilane being Si₂H₂I₄;    -   the Si—H containing iodosilane being Si₂H₃I₃;    -   the Si—H containing iodosilane being Si₂H₄I₂;    -   the Si—H containing iodosilane being Si₂H₅I;    -   the Si—H containing iodosilane having the formula        Si₂H_(x)R_(y)I_(6-x-y), wherein x=1 to 4, y=1 to 4, x+y is less        than or equal to 5, and each R is independently a C1 to C12        hydrocarbyl group, Cl, Br, or a ER′₃ group, wherein each E is        independently Si or Ge and each R′ is independently H or a C1 to        C12 hydrocarbyl group;    -   the Si—H containing iodosilane being MeSi₂HI₄;    -   the Si—H containing iodosilane being MeSi₂H₂I₃;    -   the Si—H containing iodosilane being MeSi₂H₃I₂;    -   the Si—H containing iodosilane being MeSi₂H₄I;    -   the Si—H containing iodosilane being Me₂Si₂HI₃;    -   the Si—H containing iodosilane being Me₂Si₂H₂I₂;    -   the Si—H containing iodosilane being Me₂Si₂H₃I;    -   the Si—H containing iodosilane being Me₃Si₂HI₂;    -   the Si—H containing iodosilane being Me₃Si₂H₂I;    -   the Si—H containing iodosilane being Me₄Si₂HI,    -   the Si—H containing iodosilane being EtSi₂HI₄;    -   the Si—H containing iodosilane being EtSi₂H₂I₃;    -   the Si—H containing iodosilane being EtSi₂H₃I₂;    -   the Si—H containing iodosilane being EtSi₂H₄I;    -   the Si—H containing iodosilane being Et₂Si₂HI₃;    -   the Si—H containing iodosilane being Et₂Si₂H₂I₂;    -   the Si—H containing iodosilane being Et₂Si₂H₃I;    -   the Si—H containing iodosilane being Et₃Si₂HI₂;    -   the Si—H containing iodosilane being Et₃Si₂H₂I;    -   the Si—H containing iodosilane being Et₄Si₂HI,    -   the Si—H containing iodosilane being ClSi₂HI₄;    -   the Si—H containing iodosilane being ClSi₂H₂I₃;    -   the Si—H containing iodosilane being ClSi₂H₃I₂;    -   the Si—H containing iodosilane being ClSi₂H₄I;    -   the Si—H containing iodosilane being Cl₂Si₂HI₃;    -   the Si—H containing iodosilane being Cl₂Si₂H₂I₂;    -   the Si—H containing iodosilane being Cl₂Si₂H₃I;    -   the Si—H containing iodosilane being Cl₃Si₂HI₂;    -   the Si—H containing iodosilane being Cl₃Si₂H₂I;    -   the Si—H containing iodosilane being Cl₄Si₂HI,    -   the Si—H containing iodosilane being BrSi₂HI₄;    -   the Si—H containing iodosilane being BrSi₂H₂I₃;    -   the Si—H containing iodosilane being BrSi₂H₃I₂;    -   the Si—H containing iodosilane being BrSi₂H₄I;    -   the Si—H containing iodosilane being Br₂Si₂HI₃;    -   the Si—H containing iodosilane being Br₂Si₂H₂I₂;    -   the Si—H containing iodosilane being Br₂Si₂H₃I;    -   the Si—H containing iodosilane being Br₃Si₂H₁₂;    -   the Si—H containing iodosilane being Br₃Si₂H₂I;    -   the Si—H containing iodosilane being Br₄Si₂HI,    -   the Si—H containing iodosilane being H₃SiSi₂HI₄;    -   the Si—H containing iodosilane being H₃SiSi₂H₂I₃;    -   the Si—H containing iodosilane being H₃SiSi₂H₃I₂;    -   the Si—H containing iodosilane being H₃SiSi₂H₄I;    -   the Si—H containing iodosilane being (H₃Si)₂Si₂HI₃;    -   the Si—H containing iodosilane being (H₃Si)₂Si₂H₂I₂;    -   the Si—H containing iodosilane being (H₃Si)₂Si₂H₃I;    -   the Si—H containing iodosilane being (H₃Si)₃Si₂HI₂;    -   the Si—H containing iodosilane being (H₃Si)₃Si₂H₂I;    -   the Si—H containing iodosilane being (H₃Si)₄Si₂HI,    -   the Si—H containing iodosilane being H₃GeSi₂HI₁₄;    -   the Si—H containing iodosilane being H₃GeSi₂H₂I₃;    -   the Si—H containing iodosilane being H₃GeSi₂H₃I₂;    -   the Si—H containing iodosilane being H₃GeSi₂H₄I;    -   the Si—H containing iodosilane being (H₃Ge)₂Si₂HI₃;    -   the Si—H containing iodosilane being (H₃Ge)₂Si₂H₂I₂;    -   the Si—H containing iodosilane being (H₃Ge)₂Si₂H₃I;    -   the Si—H containing iodosilane being (H₃Ge)₃Si₂HI₂;    -   the Si—H containing iodosilane being (H₃Ge)₃Si₂H₂I;    -   the Si—H containing iodosilane being (H₃Ge)₄Si₂HI,    -   the Si—H containing iodosilane being Me₃SiSi₂HI₄;    -   the Si—H containing iodosilane being Me₃SiSi₂H₂I₃;    -   the Si—H containing iodosilane being Me₃SiSi₂H₃I₂;    -   the Si—H containing iodosilane being Me₃SiSi₂H₄I;    -   the Si—H containing iodosilane being (Me₃Si)₂Si₂HI₃;    -   the Si—H containing iodosilane being (Me₃Si)₂Si₂H₂I₂;    -   the Si—H containing iodosilane being (Me₃Si)₂Si₂H₃I;    -   the Si—H containing iodosilane being (Me₃Si)₃Si₂HI₂;    -   the Si—H containing iodosilane being (Me₃Si)₃Si₂H₂I;    -   the Si—H containing iodosilane being (Me₃Si)₄Si₂HI,    -   the Si—H containing iodosilane being Me₃GeSi₂HI₄;    -   the Si—H containing iodosilane being Me₃GeSi₂H₂I₃;    -   the Si—H containing iodosilane being Me₃GeSi₂H₃I₂;    -   the Si—H containing iodosilane being Me₃GeSi₂H₄I;    -   the Si—H containing iodosilane being (Me₃Ge)₂Si₂HI₃;    -   the Si—H containing iodosilane being (Me₃Ge)₂Si₂H₂I₂;    -   the Si—H containing iodosilane being (Me₃Ge)₂Si₂H₃I;    -   the Si—H containing iodosilane being (Me₃Ge)₃Si₂HI₂;    -   the Si—H containing iodosilane being (Me₃Ge)₃Si₂H₂I;    -   the Si—H containing iodosilane being (Me₃Ge)₄Si₂HI,    -   the Si—H containing iodosilane being Me₂HSiSi₂HI₄;    -   the Si—H containing iodosilane being Me₂HSiSi₂H₂I₃;    -   the Si—H containing iodosilane being Me₂HSiSi₂H₃I₂;    -   the Si—H containing iodosilane being Me₂HSiSi₂H₄I;    -   the Si—H containing iodosilane being (Me₂HSi)₂Si₂HI₃;    -   the Si—H containing iodosilane being (Me₂HSi)₂Si₂H₂I₂;    -   the Si—H containing iodosilane being (Me₂HSi)₂Si₂H₃I;    -   the Si—H containing iodosilane being (Me₂HSi)₃Si₂HI₂;    -   the Si—H containing iodosilane being (Me₂HSi)₃Si₂H₂I;    -   the Si—H containing iodosilane being (Me₂HSi)₄Si₂HI,    -   the Si—H containing iodosilane being Me₂HGeSi₂HI₄;    -   the Si—H containing iodosilane being Me₂HGeSi₂H₂I₃;    -   the Si—H containing iodosilane being Me₂HGeSi₂H₃I₂;    -   the Si—H containing iodosilane being Me₂HGeSi₂H₄I;    -   the Si—H containing iodosilane being (Me₂HGe)₂Si₂HI₃;    -   the Si—H containing iodosilane being (Me₂HGe)₂Si₂H₂I₂;    -   the Si—H containing iodosilane being (Me₂HGe)₂Si₂H₃I;    -   the Si—H containing iodosilane being (Me₂HGe)₃Si₂HI₂;    -   the Si—H containing iodosilane being (Me₂HGe)₃Si₂H₂I;    -   the Si—H containing iodosilane being (Me₂HGe)₄Si₂HI,    -   the Si—H containing iodosilane having the formula        Si₃H_(x)I_(8-x), wherein x=1 to 8;    -   the Si—H containing iodosilane being Si₃H₇I;    -   the Si—H containing iodosilane being Si₃H₆I₂;    -   the Si—H containing iodosilane being Si₃H₅I₃;    -   the Si—H containing iodosilane being Si₃H₄I₄;    -   the Si—H containing iodosilane being Si₃H₃I₅;    -   the Si—H containing iodosilane being Si₃H₂I₆;    -   the Si—H containing iodosilane being Si₃HI₇;    -   the Si—H containing iodosilane having the formula        N(SiH_(a)I_(c))₃, wherein each a is independently 0 to 3 and        each c is independently 0 to 3, provided that at least one a and        at least one c is 1;    -   the Si—H containing iodosilane being N(SiH₃)₂(SiH₂I);    -   the Si—H containing iodosilane being N(SiH₃)₂(SiHI₂);    -   the Si—H containing iodosilane being N(SiH₃)(SiH₂I)₂;    -   the Si—H containing iodosilane being N(SiH₃)(SiHI₂)₂;    -   the Si—H containing iodosilane being N(SiHI₂)₂(SiH₂I);    -   the Si—H containing iodosilane being N(SiHI₂)(SiH₂I)₂;    -   the Si—H containing iodosilane being N(SiH₂I)₃;    -   the Si—H containing iodosilane being N(SiHI₂)₃;    -   the Si—H containing iodosilane having the formula        N(SiH_(a)R_(b)I_(c))₃, wherein each a is independently 0 to 3,        each b is independently 0 to 3, each c is independently 0 to 3,        a+b+c=3, and each R is independently a C1 to C12 hydrocarbyl        group, Cl, Br, or a ER′₃ group, wherein each E is independently        Si or Ge and each R′ is independently H or a C1 to C12        hydrocarbyl group, provided that (a) at least one x, at least        one y, and at least one z is 1, and (b) that at least one Si is        bonded to both H and I;    -   the Si—H containing iodosilane being N(SiH₃)₂(SiMeHI);    -   the Si—H containing iodosilane being N(SiH₂Me)₂(SiMeHI);    -   the Si—H containing iodosilane being N(SiHMe₂)₂(SiMeHI);    -   the Si—H containing iodosilane being N(SiMe₂H)₂(SiH₂I);    -   the Si—H containing iodosilane being N(SiMe₃)₂(SiH₂I);    -   the Si—H containing iodosilane being N(SiMe₂H)₂(SiHI₂);    -   the Si—H containing iodosilane being N(SiMe₃)₂(SiHI₂);    -   the Si—H containing iodosilanes have the formula        (SiH_(m)R_(n)I_(o))₂—CH₂ (3);    -   the Si—H containing iodosilane having the formula        (SiH_(x)I_(y))₂CH₂, wherein each x is independently 0 to 3, each        y is independently 0 to 3, provided that at least one x and at        least one y is 1;    -   the Si—H containing iodosilane being (SiH₂I)₂—CH₂;    -   the Si—H containing iodosilane being (SiHI₂)₂—CH₂;    -   the Si—H containing iodosilane being (SiH₂I)—CH₂—(SiH₃);    -   the Si—H containing iodosilane being (SiHI₂)—CH₂—(SiH₃); or    -   the Si—H containing iodosilane being (SiH₂I)—CH₂—(SiHI₂).

Also disclosed are Si-containing film forming compositions comprisingany of the Si—H containing iodosilanes listed above. The disclosedSi-containing film forming compositions comprise one or more of thefollowing aspects:

-   -   the Si-containing film forming composition comprising between        approximately 99% v/v and approximately 100% v/v of one Si—H        containing iodosilane;    -   the Si-containing film forming composition comprising between        approximately 99.5% v/v and approximately 100% v/v of one Si—H        containing iodosilane;    -   the Si-containing film forming composition comprising between        approximately 99.97% v/v and approximately 100% v/v of one Si—H        containing iodosilane;    -   the Si-containing film forming composition containing between        approximately 0 ppbw and approximately 100 ppbw Cu;    -   the Si-containing film forming composition containing between        approximately 0 ppbw and approximately 100 ppbw Ag;    -   the Si-containing film forming composition containing between        approximately 0 ppbw and approximately 100 ppbw Sb;    -   the Si-containing film forming composition containing between        approximately 0 ppbw and approximately 50 ppbw Cu;    -   the Si-containing film forming composition containing between        approximately 0 ppbw and approximately 50 ppbw Ag;    -   the Si-containing film forming composition containing between        approximately 0 ppbw and approximately 50 ppbw Sb;    -   the Si-containing film forming composition containing between        approximately 0 ppbw and approximately 10 ppbw Cu;    -   the Si-containing film forming composition containing between        approximately 0 ppbw and approximately 10 ppbw Ag;    -   the Si-containing film forming composition containing between        approximately 0 ppbw and approximately 10 ppbw Sb; or    -   the Si-containing film forming composition containing between        approximately 0 ppmw and approximately 100 ppmw C.

Also disclosed is a Si-containing film forming composition deliverydevice comprising a canister having an inlet conduit and an outletconduit and containing any of the Si-containing film formingcompositions disclosed above. The disclosed device may include one ormore of the following aspects:

-   -   an end of the inlet conduit located above a surface of the        Si-containing film forming composition and an end of the outlet        conduit located below the surface of the Si-containing film        forming composition;    -   an end of the inlet conduit located below a surface of the        Si-containing film forming composition and an end of the outlet        conduit located above the surface of the Si-containing film        forming composition;    -   further comprising a diaphragm valve on the inlet and the        outlet;    -   an internal surface of the canister being glass;    -   an internal surface of the canister being passivated stainless        steel;    -   the canister being light-resistant glass with a light resistant        coating on an external surface of the canister;    -   an internal surface of the canister being aluminum oxide;    -   further comprising one or more barrier layers on an interior        surface of the canister;    -   further comprising one to four barrier layers on an interior        surface of the canister;    -   further comprising one or two barrier layers on an interior        surface of the canister;    -   each barrier layer comprising a silicon oxide layer, silicon        nitride layer, silicon oxynitride layer, silicon carbonitride,        silicon oxycarbonitride layer, or combinations thereof;    -   wherein each barrier layer is 1 to 100 nm in thickness; or    -   wherein each barrier layer is 2 to 10 nm in thickness.

Notation and Nomenclature

Certain abbreviations, symbols, and terms are used throughout thefollowing description and claims, and include:

As used herein, the indefinite article “a” or “an” means one or morethan one.

As used herein, the terms “approximately” or “about” mean±10% of thevalue stated.

As used herein, the term “independently” when used in the context ofdescribing R groups should be understood to denote that the subject Rgroup is not only independently selected relative to other R groupsbearing the same or different subscripts or superscripts, but is alsoindependently selected relative to any additional species of that same Rgroup. For example in the formula MR¹ _(x)(NR²R³)_((4-x)), where x is 2or 3, the two or three R′ groups may, but need not be identical to eachother or to R² or to R³. Further, it should be understood that unlessspecifically stated otherwise, values of R groups are independent ofeach other when used in different formulas.

As used herein, the term “hydrocarbyl group” refers to a functionalgroup containing carbon and hydrogen; the term “alkyl group” refers tosaturated functional groups containing exclusively carbon and hydrogenatoms. The hydrocarbyl group may be saturated or unsaturated. Eitherterm refers to linear, branched, or cyclic groups. Examples of linearalkyl groups include without limitation, methyl groups, ethyl groups,n-propyl groups, n-butyl groups, etc. Examples of branched alkyls groupsinclude without limitation, iso-propyl, t-butyl. Examples of cyclicalkyl groups include without limitation, cyclopropyl groups, cyclopentylgroups, cyclohexyl groups, etc.

As used herein, the term “aryl” refers to aromatic ring compounds whereone hydrogen atom has been removed from the ring. As used herein, theterm “heterocycle” refers to a cyclic compound that has atoms of atleast two different elements as members of its ring.

As used herein, the abbreviation “Me” refers to a methyl group; theabbreviation “Et” refers to an ethyl group; the abbreviation “Pr” refersto any propyl group (i.e., n-propyl or isopropyl); the abbreviation“iPr” refers to an isopropyl group; the abbreviation “Bu” refers to anybutyl group (n-butyl, iso-butyl, t-butyl, sec-butyl); the abbreviation“tBu” refers to a tert-butyl group; the abbreviation “sBu” refers to asec-butyl group; the abbreviation “iBu” refers to an iso-butyl group;the abbreviation “Ph” refers to a phenyl group; the abbreviation “Am”refers to any amyl group (iso-amyl, sec-amyl, tert-amyl); and theabbreviation “Cy” refers to a cyclic alkyl group (cyclobutyl,cyclopentyl, cyclohexyl, etc.).

As used herein the acronym “HCDS” stands for hexachlorodisilane; theacronym “PCDS” stands for pentachlorodisilane; the acronym “OCTS” standsfor n-octyltrimethoxysilane; the acronym “TSA” stands for trisilylamineor N(SiH₃)₃.

As used herein, the term “iodosilane” means a molecule containing atleast one Si—I bond, irrespective of other bonds on the Si or of themolecule backbone. More generally, “halosilane” means a moleculecontaining at least one Si—X containing bond, wherein X is a halogenatom, irrespective of other bonds on the Si or of the molecule backbone.

As used herein, the term “Si—H containing” means a molecule containingat least one Si—H bond, irrespective of other bonds on the Si or of themolecule backbone.

As used herein, the term “coordinating solvent” means any solvent thatdonates a pair of electrons, such as solvents containing OH or NH₃groups. Exemplary coordinating solvents include amines, phosphines,ethers, and ketones.

As used herein, the acronym “LCD-TFT” stands for liquid-crystaldisplay-thin-film transistor; the acronym “MIM” stands forMetal-insulator-metal; the acronym “DRAM” stands for dynamicrandom-access memory; the acronym “FeRAM” stands for Ferroelectricrandom-access memory; the acronym “sccm” stands for standard cubiccentimeter per minute; and the acronym “GCMS” stands for GasChromatography-Mass Spectrometry.

The standard abbreviations of the elements from the periodic table ofelements are used herein. It should be understood that elements may bereferred to by these abbreviations (e.g., Si refers to silicon, N refersto nitrogen, O refers to oxygen, C refers to carbon, etc.).

Any and all ranges recited herein are inclusive of their endpoints(i.e., x=1 to 4 includes x=1, x=4, and x=any number in between),irrespective of whether the term “inclusively” is used.

BRIEF DESCRIPTION OF DRAWINGS

For a further understanding of the nature and objects of the presentinvention, reference should be made to the following detaileddescription, taken in conjunction with the accompanying figure wherein:

FIG. 1 is a schematic diagram of an apparatus in which the disclosedsynthesis methods may be performed;

FIG. 2 is a schematic diagram of an alternative apparatus in which thedisclosed synthesis methods may be performed;

FIG. 3 is a side cross-section view of one embodiment of theSi-containing film forming composition delivery device 1;

FIG. 4 is a side cross-section view of a second embodiment of theSi-containing film forming composition delivery device 1;

FIG. 5 is a side cross-section view of an exemplary embodiment of asolid precursor sublimator 100 for subliming solid Si-containing filmforming compositions;

FIG. 6 is a Gas Chromatographic/Mass Spectrometric (GC/MS) graph of theSiH₂I₂ reaction product of Example 5; and

FIG. 7 is a GC/MS graph of the reaction mixture of Example 7 after 90minutes stirring.

DETAILED DESCRIPTION

Disclosed are methods for synthesizing Si—H containing iodosilaneshaving the formula:Si_(w)H_(x)R_(y)I_(z)  (1)N(SiH_(a)R_(b)I_(c))₃  (2) or(SiH_(m)R_(n)I_(o))₂—CH₂  (3)wherein w is 1 to 3, x+y+z=2w+2, x is 1 to 2w+1, y is 0 to 2w+1, z is 1to 2w+1, each a is independently 0 to 3, each b is independently 0 to 3,each c is independently 0 to 3, a+b+c=3 provided that at least one a andat least one c is 1, each m is independently 0 to 3, each n isindependently 0 to 3, each o is independently 0 to 3, m+n+o=3 providedthat at least one m and at least one o is 1, and each R is independentlya C1 to C12 hydrocarbyl group, Cl, Br, or a ER′₃ group, wherein each Eis independently Si or Ge and each R′ is independently H or a C1 to C12hydrocarbyl group.

These compounds, such as diiodosilane (SiH₂I₂) or pentaiododisilane(Si₂HI₅), contain highly reactive Si—H groups and, in the case of y or bor n=0, do not have any organic protective groups. As a result, thesesilicon hydrides are susceptible to nucleophilic attack of the siliconhydride from coordinating solvents. See, e.g., Keinan et al., J. Org.Chem. 1987, 52, 4846-4851 (demonstrating catalytic deoxygenation ofalcohols and ethers, carbonyl conjugate addition reactions, andα-alkoxymethylation of ketones by trimethylsilyl iodine). In otherwords, special care must be taken in selection of an appropriatesolvent, when a solvent is used, because the end product may react withsolvent. This may lead to product degradation and side reactions. Thisalso limits the selection of solvents that are suitable for thesynthesis.

Finkelstein-type S_(N)2 reactions typically rely on the solubility andinsolubility of the reagent and salt byproducts, respectively, to act asa driving force in the reaction. For example, trimethylsilyl iodide(TMS-I) may be prepared by reacting trimethylsilyl chloride and analkali metal iodide salt (see Reaction Scheme 4 above) in a suitablesolvent, such as chloroform or acetonitrile. In this particular example,the trimethylsilyl chloride (TMS-Cl) and sodium iodide salts have somesolubility in these solvents, whereas the byproduct sodium chloride doesnot. The precipitation of the byproduct sodium chloride contributes tothe driving force of the reaction.

The preparation of Si_(w)H_(x)R_(y)I_(z) (e.g., SiH₂I₂ or Si₂HI₅),N(SiH_(a)R_(b)I_(c))₃ (e.g., N(SiH₃)₂(SiH₂I)), or(SiH_(m)R_(n)I_(o))₂—CH₂ (e.g., (SiH₂I)—CH₂—(SiH₃)), may be susceptibleto halogen scrambling and side reactions due to the reactivity of theSi—H bond. A coordinating solvent may exacerbate such halogen scramblingand side reactions. The reaction between dichlorosilane (DCS) andlithium iodide produces diiodosilane in the absence of a solvent atambient temperature (see infra Example 3). Non-coordinating solvents(e.g., n-pentane and chloroform) are helpful during filtration of thelithium chloride salt byproducts. Non-coordinating solvents may alsopromote the reaction by improved mixing (i.e. dilution of the reactionmass) and suppression of side reaction (heat exchange medium). Suitablenon-coordinating solvents include hydrocarbons (such as pentanes,hexanes, cyclohexane, heptanes, octanes, benzene, toluene) andchlorinated aliphatic hydrocarbons (such as chloromethane,dichloromethane, chloroform, carbon tetrachloride, acetonitrile, etc).However, the use of a chlorinated solvent is a less attractive optionsince these solvents are usually heavily regulated (permits required)and may be carcinogenic. The solvent should be selected to have asufficient difference in boiling point with the target product, suchboiling point difference being typically >20° C., and preferably >40° C.

Exemplary Si—H containing iodosilane reaction products include, but arenot limited to:

-   -   SiH_(x)I_(4-x), wherein x=1 to 3, such as SiHI₃, SiH₂I₂, or        SiH₃I;    -   SiH_(x)R_(y)I_(x-y), wherein x=1 to 2, y=1 to 2, x+y is less        than or equal to 3, and each R is independently a C1 to C12        hydrocarbyl group, Cl, Br, or a ER′₃ group, wherein each E is        independently Si or Ge and each R′ is independently H or a C1 to        C12 hydrocarbyl group, such as MeSiHI₂, MeSiH₂I, Me₂SiHI,        EtSiHI₂, EtSiH₂I, Et₂SiHI, ClSiHI₂, ClSiH₂I, Cl₂SiHI, BrSiHI₂,        BrSiH₂I, BrI₂SiHI, H₃SiSiHI₂, H₃SiSiH₂I, (H₃Si)₂SiHI, H₃GeSiHI₂,        H₃GeSiH₂I, (H₃Ge)₂SiHI, Me₃SiSiHI₂, Me₃SiSiH₂I, (Me₃Si)₂SiHI,        Me₃GeSiHI₂, Me₃GeSiH₂I, (Me₃Ge)₂SiHI, Me₂HSiSiHI₂, Me₂HSiSiH₂I,        (Me₂HSi)₂SiHI, Me₂HGeSiHI₂, Me₂HGeSiH₂I, (Me₂HGe)₂SiHI, etc.;    -   Si₂H_(x-6)I_(x), wherein x=1-5, such as Si₂HI₅, Si₂H₂I₄,        Si₂H₃I₃, Si₂H₄I₂, or Si₂H₅I, with x preferably equal to 5 (i.e.,        Si₂HI₅);    -   Si₂H_(x)R_(y)I_(6-x-y), wherein x=1 to 4, y=1 to 4, x+y is less        than or equal to 5, and each R is independently a C1 to C12        hydrocarbyl group, Cl, Br, or a ER′₃ group, wherein each E is        independently Si or Ge and each R′ is independently H or a C1 to        C12 hydrocarbyl group, such as MeSi₂HI₄, MeSi₂H₂I₃, MeSi₂H₃I₂,        MeSi₂H₄I, Me₂Si₂HI₃, Me₂Si₂H₂I₂, Me₂Si₂H₃I, Me₃Si₂HI₂,        Me₃Si₂H₂I, Me₄Si₂HI, EtSi₂HI₄, EtSi₂H₂I₃, EtSi₂H₃I₂, EtSi₂H₄I,        Et₂Si₂HI₃, Et₂Si₂H₂I₂, Et₂Si₂H₃I, Et₃Si₂HI₂, Et₃Si₂H₂I,        Et₄Si₂HI, ClSi₂H₁₄, ClSi₂H₂I₃, ClSi₂H₃I₂, ClSi₂H₄I, Cl₂Si₂HI₃,        Cl₂Si₂H₂I₂, Cl₂Si₂H₃I, Cl₃Si₂HI₂, Cl₃Si₂H₂I, Cl₄Si₂HI, BrSi₂HI₄,        BrSi₂H₂I₃, BrSi₂H₃I₂, BrSi₂H₄I, Br₂Si₂H₁₃, Br₂Si₂H₂I₂,        Br₂Si₂H₃I, Br₃Si₂HI₂, Br₃Si₂H₂I, Br₄Si₂HI, H₃SiSi₂HI₄,        H₃SiSi₂H₂I₃, H₃SiSi₂H₃I₂, H₃SiSi₂H₄I₁, (H₃Si)₂Si₂HI₃,        (H₃Si)₂Si₂H₂I₂, (H₃Si)₂Si₂H₃I, (H₃Si)₃Si₂HI₂, (H₃Si)₃Si₂H₂I,        (H₃Si)₄Si₂HI, H₃GeSi₂HI₄, H₃GeSi₂H₂I₃, H₃GeSi₂H₃I₂, H₃GeSi₂H₄I,        (H₃Ge)₂Si₂HI₃, (H₃Ge)₂Si₂H₂I₂, (H₃Ge)₂Si₂H₃I, (H₃Ge)₃Si₂HI₂,        (H₃Ge)₃Si₂H₂I, (H₃Ge)₄Si₂HI, Me₃SiSi₂H₁₄, Me₃SiSi₂H₂I₃,        Me₃SiSi₂H₃I₂, Me₃SiSi₂H₄I, (Me₃Si)₂Si₂HI₃, (Me₃Si)₂Si₂H₂I₂,        (Me₃Si)₂Si₂H₃I, (Me₃Si)₃Si₂HI₂, (Me₃Si)₃Si₂H₂I, (Me₃Si)₄Si₂HI,        Me₃GeSi₂HI₄, Me₃GeSi₂H₂I₃, Me₃GeSi₂H₃I₂, Me₃GeSi₂H₄I,        (Me₃Ge)₂Si₂HI₃, (Me₃Ge)₂Si₂H₂I₂, (Me₃Ge)₂Si₂H₃I, (Me₃Ge)₃Si₂HI₂,        (Me₃Ge)₃Si₂H₂I, (Me₃Ge)₄Si₂HI, Me₂HSiSi₂HI₄, Me₂HSiSi₂H₂I₃,        Me₂HSiSi₂H₃I₂, Me₂HSiSi₂H₄I, (Me₂HSi)₂Si₂HI₃, (Me₂HSi)₂Si₂H₂I₂,        (Me₂HSi)₂Si₂H₃I, (Me₂HSi)₃Si₂HI₂, (Me₂HSi)₃Si₂H₂I,        (Me₂HSi)₄Si₂HI, Me₂HGeSi₂HI₄, Me₂HGeSi₂H₂I₃, Me₂HGeSi₂H₃I₂,        Me₂HGeSi₂H₄I, (Me₂HGe)₂Si₂H₁₃, (Me₂HGe)₂Si₂H₂I₂,        (Me₂HGe)₂Si₂H₃I, (Me₂HGe)₃Si₂HI₂, (Me₂HGe)₃Si₂H₂I,        (Me₂HGe)₄Si₂HI, etc.;    -   Si₃H_(x-6)I_(x), wherein x=1 to 7, such as Si₃H₇I, Si₃H₆I₂,        Si₃H₅I₃, Si₃H₄I₄, Si₃H₃I₅, Si₃H₂I₆, Si₃HI₇;    -   N(SiH_(x)I_(y))₃, wherein each x is independently 0 to 3 and        each y is independently 0 to 3, provided that at least one x and        at least one y is 1, such as N(SiH₃)₂(SiH₂I), N(SiH₃)₂(SiHI₂),        N(SiH₃)(SiH₂I)₂, N(SiH₃)(SiHI₂)₂, N(SiHI₂)₂(SiH₂I),        N(SiHI₂)(SiH₂I)₂, N(SiH₂I)₃, or N(SiHI₂)₃;    -   N(SiH_(x)R_(y)I_(z))₃, wherein each x is independently 0 to 3,        each y is independently 0 to 3, each z is independently 0 to 3,        x+y+z=3, and each R is independently a C1 to C12 hydrocarbyl        group, Cl, Br, or a ER′₃ group, wherein each E is independently        Si or Ge and each R′ is independently H or a C1 to C12        hydrocarbyl group, provided that (a) at least one x, at least        one y, and at least one z is 1, and (b) that at least one Si is        bonded to both H and I, such as N(SiH₃)₂(SiMeHI),        N(SiH₂Me)₂(SiMeHI), N(SiHMe₂)₂(SiMeHI), N(SiMe₂H)₂(SiH₂I),        N(SiMe₃)₂(SiH₂I), N(SiMe₂H)₂(SiHI₂), N(SiMe₃)₂(SiHI₂), etc.; or    -   (SiH_(x)I_(y))₂CH₂, wherein each x is independently 0 to 3, each        y is independently 0 to 3, provided that at least one x and at        least one y is 1, such as (SiH₂I)₂—CH₂, (SiHI₂)₂—CH₂,        (SiH₂I)—CH₂—(SiH₃), (SiHI₂)—CH₂—(SiH₃), or (SiH₂I)—CH₂—(SiHI₂).

The Si—H containing iodosilanes are synthesized by reacting orcontacting the corresponding halosilane with an alkali metal halide, asshown:Si_(w)H_(x)R_(y)X_(z) +nMI→+Si_(w)H_(x)R_(y)I_(z) +nMX  (6)N(SiH_(a)R_(b)X_(c))₃ +nMI→N(SiH_(a)R_(b)I_(c))₃ +nMX  (7)(SiH_(m)R_(p)X_(o))₂—CH₂ +nMI→+(SiH_(m)R_(p)I_(o))₂—CH₂ +nMX  (8)wherein w=1 to 3; x=1 to 2w+1; y=0 to 2w+1; z=1 to 2w+1; x+y+z=2w+2;each a is independently 0 to 3; each b is independently 0 to 3; each cis independently 0 to 3; a+b+c=3 provided that at least one a and atleast one c is 1; each m is independently 0 to 3; each p isindependently 0 to 3; each o is independently 0 to 3; m+p+o=3 providedthat at least one m and at least one o is 1; n=1 to 4; X=Br or Cl; M=Li,Na, K, Rb, or Cs, preferably Li; and each R is independently a C1 to C12hydrocarbyl group, Cl, Br, or a ER′₃ group, wherein each E isindependently Si or Ge and each R′ is independently H or a C1 to C12hydrocarbyl group. As shown in Example 3, contact between the tworeactants may automatically initiate the chemical reaction.Alternatively, depending on the specific reactants, heat and/or mixingmay be required to initiate the reaction.

The alkali metal salts (i.e., MI) may be used in excess or in deficientquantities depending on the degree of halogen exchange desired. However,an excess of MI will favor the full substitution of the halide on thehalosilane by the iodide, reducing the amount of chlorine or bromineimpurities contained in the reaction product. The person having ordinaryskill in the art would tune the reaction stoichiometry to make partiallyiodinated molecules such as SiH₂ICl, SiHClI₂, Si₂HCl₄I, SiH₂IBr,SiHBrI₂, Si₂HBr₄I, etc.

As discussed above, the salt driven reactions dictate what reagents touse. However, unlike the prior art Finkelstein reactions, lithium iodideand lithium chloride exhibit little to no solubility in hydrocarbons orfluorocarbons. For example, the reaction of SiCl₂H₂ with two moles oflithium iodide in an aliphatic, aromatic, or chlorinated hydrocarbonwill form SiI₂H₂ and two moles of lithium chloride as the main productand salt byproduct, respectively. Both LiI and LiCl remain as solidsduring this reaction. Li and Cl form a hard acid/base pair. Li and Ihave a hard/soft acid/base mismatch. As a result, Applicants believethat formation of the insoluble LiCl may provide the driving force forthe reaction. However, the formation of SiH₂I₂ itself may partiallysolubilize LiI and help drive the reaction. As a result, it may bebeneficial to add the desired Si—H containing iodosilane product to theoriginal reaction mixture.SiH₂Cl₂ (g or l)+2LiI (s)→SiH₂I₂(l)+2LiCl (s)  (9)with g=gas, I=liquid, and s=solid. Other alkali metal salts, such assodium iodide (NaI) are useful in some cases for the preparation ofhalogen exchange products. However, NaI is less reactive than LiI in acomparable solvent and would typically require a coordinating solventfor any reaction to proceed at industrially relevant reaction rates,provided that the coordinating solvent is selected to minimize adverseimpact on product synthesis and/or yield.

In another example, the reaction of Si₂Cl₅H with five moles of sodiumiodide in a chlorinated hydrocarbon, such as chloroform, will formSi₂I₅H and five moles of sodium chloride as the main product and saltbyproduct, respectively. Formation of NaCl is the driving force for thereaction.Si₂HCl₅ (l)+5NaI (s)→+Si₂HI₅ (l)+5NaCl (s)  (10)One of ordinary skill in the art will recognize that competition betweenthe Si—Si bond cleavage and halogen exchange may require the use of theless reactive NaI or an alternative alkali metal halide, and/oralternative solvents. Product yield may be further maximized byoptimizing reaction parameters, such as removing any salt byproducts asthe reaction proceeds to further prevent halogen scrambling and sidereactions.

While the examples that follow demonstrate the disclosed synthesisprocesses using inorganic halosilane reactants, one of ordinary skill inthe art will recognize that organic Si—R groups are less reactive thanSi—X and Si—H and therefore are likely to remain undisturbed during thedisclosed synthesis processes.

The halosilane and alkali metal halide reactants may be commerciallyavailable. Alternatively, the halosilane reactant may be synthesized byreducing the corresponding fully halogenated silane (i.e.,Si_(x)R_(y)X_(2x+2-y), N(SiR_(b)X_(3-b))₃, or (SiR_(n)X_(3-n))₂—CH₂)with a standard reducing agent such as Lithium Aluminum Hydride (e.g.,LiAlH₄), NaBH₄, etc. In another alternative, the halosilane reactant maybe synthesized by reacting the corresponding silane [i.e.,Si_(x)R_(y)H_(2x+2-y), N(SiH_(a)R_(3-a))₃, or (SiH_(m)R_(3-m))₂—CH₂]with a halogenating agent, such as N-chloro, -bromo, or-iodo-succinimide in toluene for 1 to 12 hours at temperatures rangingfrom 0° C. to reflux, according to Morrison et al., J. Organomet. Chem.,92, 2, 1975, 163-168. While the form of the reactants is not critical(i.e., solid, liquid, or gas), one of ordinary skill in the art willrecognize that reactants having a larger surface area provide morereaction sites and therefore more efficient reactions. For example, afiner grain powder typically provides more reaction sites than solidbeads or chunks.

The water content of the reactants and any solvents should be minimizedto prevent formation of siloxane by-products (i.e., Si—O—Si).Preferably, the water content ranges from approximately 0% w/w toapproximately 0.001% w/w (10 ppmw). If necessary, the reactants may bedried prior to synthesis using standard techniques, such as refluxingover P₂O₅, treating by molecular sieve, or heating under vacuum (e.g.,anhydrous LiI may be produced by baking at 325° C. under vacuum for 8+hours).

The reaction vessel is made of, lined with, or treated to be a materialthat is compatible with the reactants and products. Exemplary materialsinclude passivated stainless steel, glass, perfluoroalkoxy alkanes(PFA), and polytetrafluoroethylene (PTFE). The vessel may be jacketed orplaced in a heating or cooling bath. The reaction vessel may include astirring mechanism made of a compatible material, such as glass stirringshafts, PTFE paddle stirrers, and/or PTFE coated stainless steelimpellers. The reaction vessel may also be equipped with multiple“injection ports,” pressure gauges, diaphragm valves. The reactionvessel is designed to perform the synthesis under an inert atmosphere,such as N₂ or a noble gas. Precautions to minimize the exposure of thereactants and reaction mixture to light may also be taken, such ascovering any clear glassware in tin foil. For synthesis of SiH₂I₂, ambercolored glassware is not suitable because the iron oxide coating maycontaminate the product. Additionally, the reaction vessel, stirringmechanism, and any other associated equipment, such as a Schlenk line orglovebox, should be air- and moisture-free using standard dryingtechniques, such as vacuum, inert gas flow, oven drying, etc.

As discussed above with respect to the reactants and demonstrated in theexamples that follow, the reaction vessel and any and all componentsthat come into contact with the reactants and products should have highpurity. A high purity reaction vessel is typically a vessel that iscompatible with the Si—H containing iodosilane. The high purity reactionvessel is free of impurities that may react with or contaminate the Si—Hcontaining iodosilane. Typical examples of such high purity vessels arestainless steel canisters, having low surface roughness and mirrorfinish. The low surface roughness and mirror finish is typicallyobtained by mechanical polishing and optionally by additionalelectropolishing. The high purity is typically obtained by treatmentsthat include (a) cleaning steps using dilute acids (HF, HNO₃), followedby (b) a rinsing with high purity de-ionized water to ensure thecomplete removal of traces of the acid, followed by (c) drying of thevessel. The deionized water (DIW) rinsing is typically carried out untilthe resistivity of the rinsing water reaches 100 μS/cm, and preferablybelow 25 μS/cm. The drying step may comprise purge steps using an inertgas such as He, N₂, Ar, (preferably N₂ or Ar), vacuum steps during whichthe pressure in the vessel is reduced to accelerate outgassing from thesurface, heating of the vessel, or any combination thereof.

The gas used for the purging should be of semiconductor grade, i.e. freeof contaminants such as trace moisture and oxygen (<1 ppm, preferably<10 ppb), and particles (<5 particles per litre @ 0.5 μm). The dryingstep may comprise alternate sequences of purges, during which a certainflow of gas is flown through the vessel, and vacuuming steps.Alternatively, the drying step may be carried out by constantly flowinga purge gas while maintaining a low pressure in the vessel. Theefficiency and end point of the canister drying can be assessed bymeasuring the trace H₂O level in the gas emerging from the vessel. Withan inlet gas having less than 10 ppb H₂O, the outlet gas should have amoisture content ranging from approximately 0 ppm to approximately 10ppm, preferably ranging from approximately 0 ppm to approximately 1 ppm,and more preferably ranging from approximately 0 ppb to approximately200 ppb. During the purge steps and vacuum steps, heating the vessel isknown to accelerate the drying time. Vessels are typically maintained ata temperature ranging from approximately 40° C. to approximately 150° C.during drying.

Once cleaned and dried, such high purity vessels must have a total leakrate below 1E-6 std cm3/s, preferably <1E-8 std cm3/s.

Optionally, the vessel may have internal coatings or platings to furtherreduce the risk of corrosion of or improve the stability of the productin the vessel. Exemplary coatings include those provided by Silcotek(https://www.silcotek.com) or disclosed in U.S. Pat. App. Pub. No.2016/046408. The vessel may also be passivated by exposure to asilylating agent such as silane, disilane, monochlorosilane,hexamethyldisilazane prior to the reaction and/or filling with the Si—Hcontaining iodosilane.

One of ordinary skill in the art will recognize the sources for theequipment components of the systems used to practice the disclosedmethods. Some level of customization of the components may be requiredbased upon the desired temperature range, pressure range, localregulations, etc. Exemplary equipment suppliers include Buchi GlassUster AG, Shandong ChemSta Machinery Manufacturing Co. Ltd., JiangsuShajiabang Chemical Equipment Co. Ltd, etc. As discussed above, thecomponents are preferably made of corrosion resistant materials, such asglass, glass-lined steel, or steel with corrosion resistant liners, etc.

The air- and moisture-free high purity reactor is charged with thealkali metal halide. Prior to or after addition of the alkali metalhalide to the reactor, an optional solvent that does not decompose orreact with the final product may be added as a heat exchange mediumand/or an aid in mixing and/or product extraction. Exemplary solventsinclude C3-C20 alkanes (such as propane, butane, pentane, etc.) orchlorinated hydrocarbons (such as chloromethane, dichloromethane,chloroform, carbon tetrachloride, etc.), and mixtures thereof. Asdiscussed above, the desired Si—H containing iodosilane may also be usedas a solvent. The alkali metal halide salt may be soluble in thesolvent. However, depending on the reactants, salt solubility may not bea critical factor. For example, as shown in Example 5 infra, the solidlithium iodide in pentane reacts with the liquid dichlorosilane in asolid-liquid reaction. The reaction mixture may be stirred to furtherpromote the contact between the reactants. Alternatively, the reactionmay proceed without the use of a solvent, as illustrated in Example 3infra.

The halosilane may be added to the reactor through the headspace or viasubsurface addition as a gas, liquid (condensed), or in a solution. Thehalosilane may be in gas form and added to the headspace above thelithium iodide/solvent mixture. Alternatively, the gas form of thehalosilane may condensed using a condenser and added directly to thelithium iodide/solvent mixture. In another alternative, the liquid formof the halosilane may be added from the top of the reactor using aconduit piped to the reactor. In another alternative, the gaseous orliquid form may be added below the surface of the iodine/solvent mixtureusing a reactor equipped with a dip tube plunged inside the salt/solventmixture. In the examples that follow, condensation of dichlorosilane wasdone to facilitate a more rapid reagent transfer.

The halosilane may be added in excess, stoichiometric, orsub-stoichiometric amounts, depending upon which product distribution isdesired. An excess amount of halosilane versus the metal iodide saltwill lead to a partial substitution of the halides by iodine on thehalosilane, and allow the formation of Si_(w)H_(x)R_(y)I_(z) compounds,wherein at least one R is Cl or Br. An excess of the iodide metal saltwill favor the full substitution of the iodide on the halosilane (i.e.,no R=Cl or Br).

Alternatively, the halosilane may be added to the reactor prior to theaddition of the alkali metal halide. The addition mechanisms for thehalosilane and alkali metal halide described above remain the samewhether the reactant is added to the reactor first or second.

The halosilane/alkali metal halide combination may be stirred to furtherpromote contact between the reactants. The reaction may be exothermic.In the examples that follow, the reaction mixture is stirred for asufficient time to permit the reaction to move to completion at ambienttemperature (i.e., approximately 20° C. to approximately 26° C.). Noheating was necessary in the following examples, but may be an option toaccelerate the reaction. A person of ordinary skill in the art maydetermine the most suitable temperature range depending on theindividual kinetics of each halosilane. For example, a halosilane havingpartial hydrocarbyl substitutions may require a higher reactiontemperature than a halosilane having no hydrocarbyl substituents becauseof the steric hindrance produced by the hydrocarbyl groups.

The progress of the reaction may be monitored using, for example, gaschromatography or in-situ probes such as FTIR or RAMAN probes, which arecommercially available. For a stoichiometric excess of the metal iodidesalt, the predominant reaction products are Si_(w)H_(x)R_(y)I_(z)+nMX,with minor amounts of Si_(w)H_(x)R_(y)X_(z), MI, solvent, and aSi_(w)H_(x)R_(y)(IX)_(z) intermediary reaction product, containing zamount of both I and X. For example, the SiH₂I₂ reaction mixture mayinclude the SiH₂I₂ reaction product, the LiCl reaction byproduct, someresidual SiCl₂H₂ and/or LiI reactants, solvent, and the ClSiH₂Iintermediary reaction product.

The Si—H containing iodosilane may be isolated from the reaction mixtureby filtration and distillation. Any solid impurities and the saltbyproduct may be filtered from the reaction mixture. Typical filtersinclude glass or polymer fritted filters.

Alternatively, when the salt byproduct dissolves in the solvent, themixture may be filtered to remove solid byproducts prior to furtherisolation processes. A filtration agent such as anhydrous diatomaceousearth may be employed to improve the process. Typical filters includeglass or polymer frit filters.

Occasionally, further processing may be needed to isolate the Si—Hcontaining iodosilane. For example, when the filtrate yields aheterogeneous suspension of solid material, the filtrate may then bedistilled over a short path column to isolate the Si—H containingiodosilane through a flash distillation process that removes some or allof the non-desired reaction byproducts or impurities. Alternatively, theSi—H containing iodosilane reaction product may be isolated from thefiltrate through a distillation column or by heating the filtrate toapproximately the boiling point of the non-organic silicon hydridereaction product. In another alternative, both the flash process and thedistillation column may be necessary. One of ordinary skill in the artwill recognize that the boiling point of the warmed mixture will changeas the Si—H containing iodosilane reaction product is isolated from thewarmed mixture and adjust the recovery temperature accordingly. Anyunreacted halosilane may be vented through a distillation column as ittends to be more volatile than the product obtained, owing to the highmass of iodine vs Br or Cl. One of ordinary skill in the art willrecognize that the vented halosilane may be recovered for later use ordisposal.

The disclosed methods may convert approximately 40% mol/mol toapproximately 99% mol/mol of the halosilane reactant to the Si—Hcontaining iodosilane reaction product. The isolated Si—H containingiodosilane reaction product has a purity typically ranging fromapproximately 50% mol/mol to approximately 99% mol/mol.

The Si—H containing iodosilane reaction product may be further purifiedby distillation, sublimation, or re-crystallization. Suitabledistillation methods include atmospheric fractional distillation, batchfractional distillation, or vacuum fractional distillation. The batchfractional distillation may be performed at low temperature andpressure. Alternatively, the Si—H containing iodosilane reaction productmay be purified by continuous distillation over two distillation columnsto separate the Si—H containing iodosilane reaction product from bothlow and high boiling impurities in sequential steps. The purified Si—Hcontaining iodosilane reaction products may be used as Si-containingfilm forming compositions.

The Si-containing film forming composition has a purity ranging fromapproximately 97% mol/mol to approximately 100% mol/mol, preferably fromapproximately 99% mol/mol to approximately 100% mol/mol, more preferablyfrom approximately 99.5% mol/mol to approximately 100% mol/mol, and evenmore preferably from approximately 99.97% mol/mol to approximately 100%mol/mol.

The Si-containing film forming compositions preferably comprise betweenthe detection limit and 100 ppbw of each potential metal contaminant(e.g., at least Ag, Al, Au, Ca, Cr, Cu, Fe, Mg, Mo, Ni, K, Na, Sb, Ti,Zn, etc.). More particularly, as shown in Example 11, Si-containing filmforming compositions synthesized according the disclosed methods do notrequire the use of any Sb, Ag, or Cu powder/pellet stabilizers. As aresult, the Si-containing film forming composition contains betweenapproximately 0 ppbw and approximately 100 ppbw Cu, preferably betweenapproximately 0 ppbw and 50 ppbw, and more preferably betweenapproximately 0 ppbw and 10 ppb. The ability to synthesize Si-containingfilm forming compositions that do not require Cu stabilizers isbeneficial because any Cu contamination may adversely affect theelectrical properties of the resulting Si-containing film. TheSi-containing film forming composition also contains betweenapproximately 0 ppbw and approximately 100 ppbw Sb, preferably betweenapproximately 0 ppbw and 50 ppbw, and more preferably betweenapproximately 0 ppbw and 10 ppb. The Si-containing film formingcomposition contains between approximately 0 ppbw and approximately 100ppbw Ag, preferably between approximately 0 ppbw and 50 ppbw, and morepreferably between approximately 0 ppbw and 10 ppb.

The concentration of X (wherein X=Cl, Br, or I) in the Si-containingfilm forming compositions may range from approximately 0 ppmw toapproximately 100 ppmw, and more preferably from approximately 0 ppmwand to approximately 10 ppmw.

When y or b or n=0 (i.e., the Si-containing film forming compositions donot have any organic protective groups), the Si-containing film formingcompositions comprise between approximately 0 ppmw and approximately 100ppmw C. Depending upon the type of Si-containing film being deposited,carbon incorporation may be highly undesired because small amounts of Cin the film result in large changes in film properties. Film propertiesthat may be strongly affected by small levels of C incorporation includewet etch rate, leakage current, film stress, and/or Young's modulus. Asa result, controlling the amount of C in the Si-containing film isdesirable. Synthesizing a Si-containing film forming composition that isC free provides more flexibility in engineering the desiredSi-containing film composition. Alternative synthetic methods thatutilize organic ligands have a much higher probability of containing Cimpurities in the final product, irrespective of the purification stepsperformed following the synthesis reaction. The methods disclosed hereindo not use any organic ligands when y or b or n=0 and therefore avoidthis potential contamination source, providing high reliability andsimilarity of product from run to run.

As shown in the examples below, the purified product may be analyzed bygas chromatography mass spectrometry (GCMS). The structure of theproduct may be confirmed by ¹H, ¹³C and/or ²⁹Si NMR.

As discussed in detail above and illustrated in the examples thatfollow, the Si-containing film forming composition must be stored in aclean dry storage vessel with which it does not react in order tomaintain its purity.

FIG. 1 is an exemplary system suitable to perform the disclosed methods.Air may be removed from various parts of the system (e.g., reactor 1,vessel 8, boiler 6) by an inert gas 9 (e.g., nitrogen, argon, etc.). Theinert gas 9 may also serve to pressurize optional solvent vessel 11 topermit solvent delivery to reactor 1. Nitrogen, refrigerated ethanol, anacetone/dry ice mixture, or heat transfer agents such as monoethyleneglycol (MEG) may be used to cool various parts of the system (e.g.,reactor 1, distillation column 27, condenser 57).

The reactor 1 may be maintained at the desired temperature by jacket 2.The jacket 2 has an inlet 21 and an outlet 22. Inlet 21 and outlet 22may be connected to a heat exchanger/chiller 23 and/or pump (not shown)to provide recirculation of the cooling fluid. Alternatively, if thebatch size is small enough and the mixing time short enough, jacket 2may not require inlet 21 and outlet 22 because the thermal fluid may besufficiently cold for the duration of the reaction. In anotheralternative, and as discussed above, jacketed temperature control maynot be necessary and these four components removed from the system(i.e., 2, 21, 22 and 23).

The reactants [optional solvent (such as pentane) stored in solventvessel 11 and halosilane (such as ethyldichlorosilane) stored inhalosilane vessel 24] are added to reactor 1 via optional solvent line14 and halosilane line 25, respectively. The optional solvent andhalosilane may be added to the reactor 1 via a liquid metering pump (notshown), such as a diaphragm pump, peristaltic pump, or syringe pump. Thealkali metal halide (such as LiI), stored in alkali metal halide vessel13, may be added to the reactor 1 via gravity flow or suspended in asolvent compatible with the Si—H containing iodosilane reaction productand introduced into the reactor in a manner analogous to that of thesolvent and halosilane (i.e., via alkali metal halide line 16). Thecontact between the reactants may be further promoted by mixing with animpeller 17 a turned by motor 17 b to form mixture 26. Preferably, themixing is performed under an inert atmosphere at approximatelyatmospheric pressure. A temperature sensor (not shown) may be used tomonitor the temperature of the contents of the reactor 1.

Upon completion of the addition, the progress of the reaction may bemonitored using, for example, gas chromatography. Upon completion of thereaction, the mixture 26 may be removed from reactor 1 via drain 19through filter 3 to still pot container 4. The predominant reactionproducts are ethyldiiodosilane (EtSiHI₂—a liquid at standard temperatureand pressure) and LiCl (a solid at standard temperature and pressure),with minor amounts of LiI and EtSiIClH impurities. As a result,filtration isolates the liquid ethyldiiodosilane product from the LiClreaction byproduct. In this embodiment, reactor 1 will most likely belocated above filter 3 to best use the benefits of gravity. As the MXreaction byproduct (X=Cl, Br), for example LiCl, (not shown) issuspended in the mixture 26, clogging of the reactor 1 is not a problem.

The filtered stirred mixture (filtrate)(not shown) may be collected incontainers (not shown) and transported to a new location prior toperformance of the next process steps. Alternatively, the filtrate mayimmediately be directed to a still pot container 4 to further isolatethe reaction product from any solvent or other impurities using heater28. The filtrate is warmed by heater 28. The heat forces any volatilesolvent through distillation column 27 and vent 43. Subsequently, theisolated reaction product is collected in vessel 8.

Once again, vessel 8 may be transported to a new location prior toperformance of the next process steps. The isolated reaction product maybe transferred from vessel 8 to boiler 6 for further purification, ifnecessary. Boiler 6 is heated by heater 29. The isolated reactionproduct is purified by fractional distillation using distillation tower53, condenser 57, and reflux divider 54. The purified reaction productis collected in collection tank 7. Collection tank 7 includes vent 60.

FIG. 2 is an alternate exemplary system suitable to perform thedisclosed methods. In this alternative, reactor 1 also serves as thestill pot container 4 of FIG. 1. This embodiment may be useful forsynthesis of large batches of Si—H containing iodosilanes. Aftersufficient mixing, the cooling medium (not shown) in jacket 2 isreplaced by a heating medium (not shown). One of ordinary skill in theart will recognize that “replacement” of the cooling medium will not benecessary if the cooling medium is also capable of acting as both aheating and cooling medium (e.g., MEG). Instead, the temperature of themedium may be changed via, for example, heat exchanger 23.

The volatile solvent may be separated from the mixture 26 throughdistillation column 27 and vent 43. Subsequently, Si—H containingiodosilane is isolated in vessel 8. The remaining solvent/salt mixturemay be removed from reactor 1 via drain 19 with the salt collected onfilter 3. Once again, vessel 8 may be transported to a new locationprior to performance of the next process steps. The Si—H containingiodosilane may be transferred from vessel 8 to boiler 6 for furtherpurification, if necessary. Boiler 6 is heated by heater 29. The Si—Hcontaining iodosilane is purified by fractional distillation usingdistillation tower 53, condenser 57, and reflux divider 54. The purifiedSi—H containing iodosilane is collected in collection tank 7. Collectiontank 7 includes vent 60.

In another alternative, the reaction may be performed in a continuousreactor by passing the halosilane reactant (in gas or liquid form ordiluted in a solvent) and the alkali metal iodide reactant (possiblysuspended in a solvent) through a flow through reactor at a controlledresidence time and temperatures. The flow of each reagent may becontrolled by metering pumps such as peristaltic pumps. The reactionmixture may be collected in a receiving vessel and the Si—H containingiodosilane isolated as in the batch synthesis example above.Alternatively, the solid fraction may be removed in line, using forinstance a centrifuge pump (commercially available). In anotheralternative, the Si—H containing iodosilane product may be isolated fromany solvent(s) by continuously feeding the filtered fraction to acontinuous distillation unit.

The advantages of the disclosed synthesis methods are as follows:

-   -   A catalyst free process, which helps reduce cost, contamination        and product isolation issues;    -   Essentially eliminates a majority of side reactions associated        with the prior art reaction using an iodine reactant, which        forms lower and higher-order iodosilanes as impurities;    -   Does not produce a HX intermediary reaction product, which may        contribute to side reactions and increased impurity profile and,        as a result, the resulting product does not require the prior        art Ag, Cu or Sb stabilizer;    -   When y or b or n=0, no carbon containing impurities are        produced, which may negatively affect the properties of the        resulting Si-containing film;    -   Many of the starting materials are inexpensive and readily        available;    -   One step-one pot reactions;    -   The process may be solventless;    -   Simple purification;    -   Low reaction exotherm;    -   May be performed at ambient temperature (i.e., approximately        20° C. to approximately 26° C.); and    -   The waste generation is minimal and environmentally benign.

All of the above are advantageous from the standpoint of developing ascalable industrial process. Additionally, the resulting product is morestable than products made using X₂ or HX reactants. As a result, thereaction product maintains purity levels suitable for the semiconductorindustry without the use of stabilizers, such as Cu, which may adverselyaffect the electrical properties of the deposited films.

Also disclosed are methods of using the disclosed Si-containing filmforming compositions for vapor deposition methods. The disclosed methodsprovide for the use of the Si-containing film forming compositions fordeposition of silicon-containing films. The disclosed methods may beuseful in the manufacture of semiconductor, photovoltaic, LCD-TFT, orflat panel type devices. The method includes: introducing the vapor ofthe disclosed Si-containing film forming compositions into a reactorhaving a substrate disposed therein and depositing at least part of thedisclosed Si—H containing iodosilane onto the substrate via a depositionprocess to form a Si-containing layer.

The disclosed methods also provide for forming a bimetal-containinglayer on a substrate using a vapor deposition process and, moreparticularly, for deposition of SiMO_(x) or SiMN_(x) films, wherein xmay be 0-4 and M is Ta, Nb, V, Hf, Zr, Ti, Al, B, C, P, As, Ge,lanthanides (such as Er), or combinations thereof.

The disclosed methods of forming silicon-containing layers on substratesmay be useful in the manufacture of semiconductor, photovoltaic,LCD-TFT, or flat panel type devices. The disclosed Si—H containingiodosilanes may deposit Si-containing films using any vapor depositionmethods known in the art. Examples of suitable vapor deposition methodsinclude chemical vapor deposition (CVD) or atomic layer deposition(ALD). Exemplary CVD methods include thermal CVD, plasma enhanced CVD(PECVD), pulsed CVD (PCVD), low pressure CVD (LPCVD), sub-atmosphericCVD (SACVD) or atmospheric pressure CVD (APCVD), flowable CVD (f-CVD),metal organic chemical vapor deposition (MOCVD), hot-wire CVD (HWCVD,also known as cat-CVD, in which a hot wire serves as an energy sourcefor the deposition process), radicals incorporated CVD, and combinationsthereof. Exemplary ALD methods include thermal ALD, plasma enhanced ALD(PEALD), spatial isolation ALD, hot-wire ALD (HWALD), radicalsincorporated ALD, and combinations thereof. Super critical fluiddeposition may also be used. The deposition method is preferably ALD,spatial ALD, or PE-ALD in order to provide suitable step coverage andfilm thickness control.

The vapor of the Si-containing film forming composition is introducedinto a reaction chamber containing a substrate. The temperature and thepressure within the reaction chamber and the temperature of thesubstrate are held at conditions suitable for vapor deposition of atleast part of the Si—H containing iodosilane onto the substrate. Inother words, after introduction of the vaporized composition into thechamber, conditions within the chamber are such that at least part ofthe vaporized precursor deposits onto the substrate to form thesilicon-containing film. A co-reactant may also be used to help information of the Si-containing layer.

The reaction chamber may be any enclosure or chamber of a device inwhich deposition methods take place, such as, without limitation, aparallel-plate type reactor, a cold-wall type reactor, a hot-wall typereactor, a single-wafer reactor, a multi-wafer reactor, or other suchtypes of deposition systems. All of these exemplary reaction chambersare capable of serving as an ALD reaction chamber. The reaction chambermay be maintained at a pressure ranging from about 0.5 mTorr to about760 Torr. In addition, the temperature within the reaction chamber mayrange from about 20° C. to about 700° C. One of ordinary skill in theart will recognize that the temperature may be optimized through mereexperimentation to achieve the desired result.

The temperature of the reactor may be controlled by either controllingthe temperature of the substrate holder and/or controlling thetemperature of the reactor wall. Devices used to heat the substrate areknown in the art. The reactor wall may be heated to a sufficienttemperature to obtain the desired film at a sufficient growth rate andwith desired physical state and composition. A non-limiting exemplarytemperature range to which the reactor wall may be heated includes fromapproximately 20° C. to approximately 700° C. When a plasma depositionprocess is utilized, the deposition temperature may range fromapproximately 20° C. to approximately 550° C. Alternatively, when athermal process is performed, the deposition temperature may range fromapproximately 300° C. to approximately 700° C.

Alternatively, the substrate may be heated to a sufficient temperatureto obtain the desired silicon-containing film at a sufficient growthrate and with desired physical state and composition. A non-limitingexemplary temperature range to which the substrate may be heatedincludes from 150° C. to 700° C. Preferably, the temperature of thesubstrate remains less than or equal to 500° C.

The type of substrate upon which the silicon-containing film will bedeposited will vary depending on the final use intended. A substrate isgenerally defined as the material on which a process is conducted. Thesubstrates include, but are not limited to, any suitable substrate usedin semiconductor, photovoltaic, flat panel, or LCD-TFT devicemanufacturing. Examples of suitable substrates include wafers, such assilicon, silica, glass, Ge, or GaAs wafers. The wafer may have one ormore layers of differing materials deposited on it from a previousmanufacturing step. For example, the wafers may include silicon layers(crystalline, amorphous, porous, etc.), silicon oxide layers, siliconnitride layers, silicon oxy nitride layers, carbon doped silicon oxide(SiCOH) layers, or combinations thereof. Additionally, the wafers mayinclude copper layers, tungsten layers or metal layers (e.g. platinum,palladium, nickel, rhodium, or gold). The wafers may include barrierlayers, such as manganese, manganese oxide, tantalum, tantalum nitride,etc. The layers may be planar or patterned. In some embodiments, thesubstrate may be coated with a patterned photoresist film. In someembodiments, the substrate may include layers of oxides which are usedas dielectric materials in MIM, DRAM, or FeRam technologies (forexample, ZrO₂ based materials, HfO₂ based materials, TiO₂ basedmaterials, rare earth oxide based materials, ternary oxide basedmaterials, etc.) or from nitride-based films (for example, TaN) that areused as electromigration barrier and adhesion layer between copper andthe low-k layer. The disclosed processes may deposit thesilicon-containing layer directly on the wafer or directly on one ormore than one (when patterned layers form the substrate) of the layerson top of the wafer. Furthermore, one of ordinary skill in the art willrecognize that the terms “film” or “layer” used herein refers to athickness of some material laid on or spread over a surface and that thesurface may be a trench or a line. Throughout the specification andclaims, the wafer and any associated layers thereon are referred to assubstrates. The actual substrate utilized may also depend upon thespecific precursor embodiment utilized. In many instances though, thepreferred substrate utilized will be selected from hydrogenated carbon,TiN, SRO, Ru, and Si type substrates, such as polysilicon or crystallinesilicon substrates.

The substrate may be patterned to include vias or trenches having highaspect ratios. For example, a conformal Si-containing film, such as SiNor SiO₂, may be deposited using any ALD technique on a through siliconvia (TSV) having an aspect ratio ranging from approximately 20:1 toapproximately 100:1.

The Si-containing film forming compositions may be supplied neat.Alternatively, the Si-containing film forming compositions may furthercomprise a solvent suitable for use in vapor deposition. The solvent maybe selected from, among others, C₁-C₁₆ saturated or unsaturatedhydrocarbons.

For vapor deposition, the Si-containing film forming compositions areintroduced into a reactor in vapor form by conventional means, such astubing and/or flow meters. The vapor form may be produced by vaporizingthe Si-containing film forming compositions through a conventionalvaporization step such as direct liquid injection, direct vapor draw inthe absence of a carrier gas, by bubbling a carrier gas through theliquid, or by evaporating vapors in a carrier gas without bubblingthrough the liquid. When the precursor is solid at room temperature, asublimator may be used, such as the one disclosed in PCT PublicationWO2009/087609 to Xu et al. The Si-containing film forming compositionsmay be fed in liquid state to a vaporizer (Direct Liquid Injection)where it is vaporized and mixed with a carrier gas before it isintroduced into the reactor. Alternatively, the Si-containing filmforming compositions may be vaporized by passing a carrier gas into acontainer containing the composition or by bubbling the carrier gas intothe composition. The carrier gas may include, but is not limited to, Ar,He, or N₂, and mixtures thereof. The carrier gas and composition arethen introduced into the reactor as a vapor.

The Si-containing film forming compositions may be delivered to thereactor or vapor deposition chamber by the Si-containing film formingcomposition delivery devices of FIGS. 3-5. FIGS. 3-5 show threeexemplary embodiments of Si-containing film forming composition deliverydevices. As discussed in detail above and illustrated in the examplesthat follow, the delivery devices must be clean and dry and made of amaterial with which the Si-containing film forming composition does notreact.

FIG. 3 is a side view of one embodiment of the Si-containing filmforming composition delivery device 101. In FIG. 3, the disclosedSi-containing film forming compositions 110 are contained within acontainer 200 having two conduits, an inlet conduit 300 and an outletconduit 400. One of ordinary skill in the art will recognize that thecontainer 200, inlet conduit 300, and outlet conduit 400 aremanufactured to prevent the escape of the gaseous form of theSi-containing film forming composition 110, even at elevated temperatureand pressure.

The outlet conduit 400 of the delivery device 101 fluidly connects tothe reactor (not shown) or other components between the delivery deviceand the reactor, such as a gas cabinet, via valve 700. Preferably, thecontainer 200, inlet conduit 300, valve 600, outlet conduit 400, andvalve 700 are made of passivated 316L EP or 304 passivated stainlesssteel. However, one of ordinary skill in the art will recognize thatother non-reactive materials may also be used in the teachings herein.

In FIG. 3, the end 800 of inlet conduit 300 is located above the surfaceof the Si-containing film forming composition 110, whereas the end 900of the outlet conduit 400 is located below the surface of theSi-containing film forming composition 110. In this embodiment, theSi-containing film forming composition 110 is preferably in liquid form.An inert gas, including but not limited to nitrogen, argon, helium, andmixtures thereof, may be introduced into the inlet conduit 300. Theinert gas pressurizes the container 200 so that the liquid Si-containingfilm forming composition 110 is forced through the outlet conduit 400and to the reactor (not shown). The reactor may include a vaporizerwhich transforms the liquid Si-containing film forming composition 110into a vapor, with or without the use of a carrier gas such as helium,argon, nitrogen or mixtures thereof, in order to deliver the vapor tothe substrate on which the film will be formed. Alternatively, theliquid Si-containing film forming composition 110 may be delivereddirectly to the wafer surface as a jet or aerosol.

FIG. 4 is a side view of a second embodiment of the Si-containing filmforming composition delivery device 101. In FIG. 4, the end 800 of inletconduit 300 is located below the surface of the Si-containing filmforming composition 110, whereas the end 900 of the outlet conduit 400is located above the surface of the Si-containing film formingcomposition 110. FIG. 4 also includes an optional heating element 140,which may increase the temperature of the Si-containing film formingcomposition 110. In this embodiment, the Si-containing film formingcomposition 110 may be in solid or liquid form. An inert gas, includingbut not limited to nitrogen, argon, helium, and mixtures thereof, isintroduced into the inlet conduit 300. The inert gas bubbles through theSi-containing film forming composition 110 and carries a mixture of theinert gas and vaporized Si-containing film forming composition 110 tothe outlet conduit 400 and on to the reactor.

FIGS. 3 and 4 include valves 600 and 700. One of ordinary skill in theart will recognize that valves 600 and 700 may be placed in an open orclosed position to allow flow through conduits 300 and 400,respectively. Either delivery device 101 in FIGS. 3 and 4, or a simplerdelivery device having a single conduit terminating above the surface ofany solid or liquid present, may be used if the Si-containing filmforming composition 110 is in vapor form or if sufficient vapor pressureis present above the solid/liquid phase. In this case, the Si-containingfilm forming composition 110 is delivered in vapor form through theconduit 300 or 400 simply by opening the valve 600 in FIG. 3 or 700 inFIG. 4. The delivery device 101 may be maintained at a suitabletemperature to provide sufficient vapor pressure for the Si-containingfilm forming composition 110 to be delivered in vapor form, for exampleby the use of an optional heating element 140.

While FIGS. 3 and 4 disclose two embodiments of the Si-containing filmforming composition delivery device 101, one of ordinary skill in theart will recognize that the inlet conduit 300 and outlet conduit 400 mayalso both be located above or below the surface of the Si-containingfilm forming composition 110 without departing from the disclosureherein. Furthermore, inlet conduit 300 may be a filling port.

The vapors of solid forms of the Si-containing film forming compositionsmay be delivered to the reactor using a sublimator. FIG. 5 shows oneembodiment of an exemplary sublimator 100. The sublimator 100 comprisesa container 33. Container 33 may be a cylindrical container, oralternatively, may be any shape, without limitation. The container 33 isconstructed of materials such as passivated stainless steel, aluminumoxide, glass, and other chemically compatible materials, withoutlimitation. In certain instances, the container 33 is constructed ofanother metal or metal alloy, without limitation. In certain instances,the container 33 has an internal diameter from about 8 centimeters toabout 55 centimeters and, alternatively, an internal diameter from about8 centimeters to about 30 centimeters. As understood by one skilled inthe art, alternate configurations may have different dimensions.

Container 33 comprises a sealable top 15, sealing member 18, and gasket20. Sealable top 15 is configured to seal container 33 from the outerenvironment. Sealable top 15 is configured to allow access to thecontainer 33. Additionally, sealable top 15 is configured for passage ofconduits into container 33. Alternatively, sealable top 15 is configuredto permit fluid flow into container 33. Sealable top 15 is configured toreceive and pass through a conduit comprising a dip tube 92 to remain influid contact with container 33. Dip tube 92 having a control valve 90and a fitting 95 is configured for flowing carrier gas into container33. In certain instances, dip tube 92 extends down the center axis ofcontainer 33. Further, sealable top 15 is configured to receive and passthrough a conduit comprising outlet tube 12. The carrier gas and vaporof the Si-containing film forming composition is removed from container33 through the outlet tube 12. Outlet tube 12 comprises a control valve10 and fitting 5. In certain instances, outlet tube 12 is fluidlycoupled to a gas delivery manifold, for conducting carrier gas from thesublimator 100 to the reactor.

Container 33 and sealable top 15 are sealed by at least two sealingmembers 18; alternatively, by at least about four sealing members. Incertain instance, sealable top 15 is sealed to container 33 by at leastabout eight sealing members 18. As understood by one skilled in the art,sealing member 18 releasably couples sealable top 15 to container 33,and forms a gas resistant seal with gasket 20. Sealing member 18 maycomprise any suitable means known to one skilled in the art for sealingcontainer 33. In certain instances, sealing member 18 comprises athumbscrew.

As illustrated in FIG. 5, container 33 further comprises at least onedisk disposed therein. The disk comprises a shelf, or horizontalsupport, for solid material. In certain embodiments, an interior disk 30is disposed annularly within the container 33, such that the disk 30includes an outer diameter or circumference that is less than the innerdiameter or circumference of the container 33, forming an opening 31. Anexterior disk 86 is disposed circumferentially within the container 33,such that the disk 86 comprises an outer diameter or circumference thatis the same, about the same, or generally coincides with the innerdiameter of the container 33. Exterior disk 86 forms an opening 87disposed at the center of the disk. A plurality of disks is disposedwithin container 33. The disks are stacked in an alternating fashion,wherein interior disks 30, 34, 36, 44 are vertically stacked within thecontainer with alternating exterior disks 62, 78, 82, 86. Inembodiments, interior disks 30, 34, 36, 44 extend annularly outward, andexterior disks 62, 78, 82, 86 extend annularly toward the center ofcontainer 33. As illustrated in the embodiment of FIG. 5, interior disks30, 34, 36, 44 are not in physical contact with exterior disks 62, 78,82, 86.

The assembled sublimator 100 comprises interior disks 30, 34, 36, 44comprising aligned and coupled support legs 50, interior passage 51,concentric walls 40, 41, 42, and concentric slots 47, 48, 49. Theinterior disks 30, 34, 36, 44 are vertically stacked, and annularlyoriented about the dip tube 92. Additionally, the sublimator comprisesexterior disks 62, 78, 82, 86. As illustrated in FIG. 5, the exteriordisks 62, 78, 82, 86 should be tightly fit into the container 33 for agood contact for conducting heat from the container 33 to the disks 62,78, 82, 86. Preferably, the exterior disks 62, 78, 82, 86 are coupledto, or in physical contact with, the inner wall of the container 33.

As illustrated, exterior disks 62, 78, 82, 86 and interior disks 30, 34,36, 44 are stacked inside the container 33. When assembled in container33 to form sublimator 100, the interior disks 30, 34, 36, 44 form outergas passages 31, 35, 37, 45 between the assembled exterior disks 62, 78,82, 86. Further, exterior disks 62, 78, 82, 86 form inner gas passages56, 79, 83, 87 with the support legs of the interior disks 30, 34, 36,44. The concentric walls 40, 41, 42 of interior disks 30, 34, 36, 44form the grooved slots for holding solid precursors. Exterior disks 62,78, 82, 86 comprise walls 68, 69, 70 for holding solid precursors.During assembly, the solid precursors are loaded into the concentricslots 47, 48, 49 of interior disks 30, 34, 36, 44 and annular slots 64,65, 66 of exterior disks 62, 78, 82, 86.

Solid powders and/or granular particles of sizes less than about 1centimeter, alternatively less than about 0.5 centimeter, andalternatively less than about 0.1 centimeter are loaded into theconcentric slots 47, 48, 49 of interior disks 30, 34, 36, 44 and annularslots 64, 65, 66 of exterior disks 62, 78, 82, 86. The solid precursorsare loaded into the annular slots of each disk by any method suitablefor uniform distribution of solid in the annular slots. Suitable methodsinclude direct pour, using a scoop, using a funnel, automated measureddelivery, and pressurized delivery, without limitation. Depending on thechemical properties of the solid precursor materials, loading may beconducted in a sealed environment. Additionally, inert gas atmosphereand/or pressurization in a sealed box may be implemented for thosetoxic, volatile, oxidizable, and/or air sensitive solids. Each diskcould be loaded after setting the disk in the container 33. A morepreferred procedure is to load the solid prior to setting the disk intocontainer 33. The total weight of solid precursor loaded into thesublimator may be recorded by weighing the sublimator before and afterloading process. Further, consumed solid precursor may be calculated byweighing the sublimator after the vaporization and deposition process.

Dip tube 92, having the control valve 90 and the fitting 95, ispositioned in the interior passage 51 of the aligned and coupled supportlegs of the interior disks 30, 34, 36, 44. Thus, dip tube 92 passesthrough interior passage 51 vertically toward bottom 58 of container 33.The dip tube end 55 is disposed proximal to the bottom 58 of containerat/or above the gas windows 52. Gas windows 52 are disposed in bottominterior disk 44. The gas windows 52 are configured to allow carrier gasflow out of the dip tube 92. In the assembled sublimator 100, a gaspassageway 59 is formed by the bottom 58 of the container 33, and thebottom interior disk 44. In certain instances, gas passageway 59 isconfigured to heat carrier gas.

In operation, the carrier gas is preheated prior to introduction intothe container 33 via dip tube 92. Alternatively, the carrier gas can beheated while it flows through the gas passageway 59 by the bottom 58 ofthe container 33. Bottom 58 of the container 33 is thermally coupledand/or heated by an external heater consistently with the teachingsherein. The carrier gas then passes through the outer gas passage 45that is formed by the concentric wall 42 of the interior disk 44 and theoutside wall 61 of the exterior disk 62. The outer gas passage 45 leadsto the top of the interior disk 44. The carrier gas continuously flowsover the top of the solid precursors loaded into the concentric slots47, 48, and 49. Sublimed solid vapor from concentric slots 47, 48, 49 ismixed with carrier gas and is flowed vertically upward through container33.

While FIG. 5 discloses one embodiment of a sublimator capable ofdelivering the vapor of any solid Si-containing film forming compositionto the reactor, one of ordinary skill in the art will recognize thatother sublimator designs may also be suitable, without departing fromthe teachings herein. Finally, one of ordinary skill in the art willrecognize that the disclosed Si-containing film forming composition maybe delivered to semiconductor processing tools using other deliverydevices, such as the ampoules disclosed in WO 2006/059187 to Jurcik etal., without departing from the teachings herein.

If necessary, the Si-containing film forming composition deliverydevices of FIGS. 3-5 may be heated to a temperature that permits theSi-containing film forming composition to be in its liquid phase and tohave a sufficient vapor pressure. The delivery device may be maintainedat temperatures in the range of, for example, 0-150° C. Those skilled inthe art recognize that the temperature of the delivery device may beadjusted in a known manner to control the amount of Si-containing filmforming composition vaporized.

In addition to the disclosed composition, a reaction gas may also beintroduced into the reactor. The reaction gas may be an oxidizing agentsuch as O₂; O₃; H₂O; H₂O₂; oxygen containing radicals such as O. or OH.;NO; NO₂; carboxylic acids such as formic acid, acetic acid, propionicacid; radical species of NO, NO₂, or the carboxylic acids;para-formaldehyde; and mixtures thereof. Preferably, the oxidizing agentis selected from the group consisting of O₂, O₃, H₂O, H₂O₂, oxygencontaining radicals thereof such as O. or OH., and mixtures thereof.Preferably, when an ALD process is performed, the co-reactant is plasmatreated oxygen, ozone, or combinations thereof. When an oxidizing gas isused, the resulting silicon containing film will also contain oxygen.

Alternatively, the reaction gas may H₂, NH₃, (SiH₃)₃N, hydridosilanes(such as SiH₄, Si₂H₆, Si₃He, Si₄H₁₀, Si₅H₁₀, Si₆H₁₂), chlorosilanes andchloropolysilanes (such as SiHCl₃, SiH₂Cl₂, SiH₃Cl, Si₂Cl₆, Si₂HCl₅,Si₃Cl₈), alkylsilanes (such as Me₂SiH₂, Et₂SiH₂, MeSiH₃, EtSiH₃),hydrazines (such as N₂H₄, MeHNNH₂, MeHNNHMe), organic amines (such asNMeH₂, NEtH₂, NMe₂H, NEtH₂, NMe₃, NEt₃, (SiMe₃)₂NH), diamines such asethylene diamine, dimethylethylene diamine, tetramethylethylene diamine,pyrazoline, pyridine, B-containing molecules (such as B₂H₆,trimethylboron, triethylboron, borazine, substituted borazine,dialkylaminoboranes), alkyl metals (such as trimethylaluminum,triethylaluminum, dimethylzinc, diethylzinc), radical species thereof,or mixtures thereof. When H₂ or an inorganic Si containing gas is used,the resulting silicon containing film may be pure Si.

Alternatively, the reaction gas may be a hydrocarbon, saturated orunsaturated, linear, branched or cyclic, such as but not limited toethylene, acetylene, propylene, isoprene, cyclohexane, cyclohexene,cyclohexadiene, pentene, pentyne, cyclopentane, butadiene, cyclobutane,terpinene, octane, octene, or combinations thereof.

The reaction gas may be treated by a plasma, in order to decompose thereaction gas into its radical form. N₂ may also be utilized as areducing agent when treated with plasma. For instance, the plasma may begenerated with a power ranging from about 50 W to about 500 W,preferably from about 100 W to about 200 W. The plasma may be generatedor present within the reactor itself. Alternatively, the plasma maygenerally be at a location removed from the reactor, for instance, in aremotely located plasma system. One of skill in the art will recognizemethods and apparatus suitable for such plasma treatment.

The desired silicon-containing film also contains another element, suchas, for example and without limitation, B, P, As, Zr, Hf, Ti, Nb, V, Ta,Al, Si, or Ge.

The Si-containing film forming composition and one or more co-reactantsmay be introduced into the reaction chamber simultaneously (chemicalvapor deposition), sequentially (atomic layer deposition), or in othercombinations. For example, the vapor of the Si-containing film formingcomposition may be introduced in one pulse and two additional metalsources may be introduced together in a separate pulse (modified atomiclayer deposition). Alternatively, the reaction chamber may alreadycontain the co-reactant prior to introduction of the Si-containing filmforming composition. The co-reactant may be passed through a plasmasystem localized within or remote from the reaction chamber, anddecomposed to radicals. Alternatively, the Si-containing film formingcomposition may be introduced to the reaction chamber continuously whileother precursors or reactants are introduced by pulse (pulsed-chemicalvapor deposition). In another alternative, the Si-containing filmforming composition and one or more co-reactants may be simultaneouslysprayed from a shower head under which a susceptor holding severalwafers is spun (spatial ALD).

In one non-limiting exemplary atomic layer deposition process, the vaporphase of the Si-containing film forming composition is introduced intothe reaction chamber, where it is contacted with a suitable substrate.Excess composition may then be removed from the reaction chamber bypurging and/or evacuating the reaction chamber. An oxygen source isintroduced into the reaction chamber where it reacts with the absorbedSi—H containing iodosilane in a self-limiting manner. Any excess oxygensource is removed from the reaction chamber by purging and/or evacuatingthe reaction chamber. If the desired film is a silicon oxide film, thistwo-step process may provide the desired film thickness or may berepeated until a film having the necessary thickness has been obtained.

Alternatively, if the desired film is a silicon metal/metalloid oxidefilm (i.e., SiMO_(x), wherein x may be 0-4 and M is B, Zr, Hf, Ti, Nb,V, Ta, Al, Si, Ga, Ge, or combinations thereof), the two-step processabove may be followed by introduction of a vapor of a metal- ormetalloid-containing precursor into the reaction chamber. The metal- ormetalloid-containing precursor will be selected based on the nature ofthe silicon metal/metalloid oxide film being deposited. Afterintroduction into the reaction chamber, the metal- ormetalloid-containing precursor is contacted with the substrate. Anyexcess metal- or metalloid-containing precursor is removed from thereaction chamber by purging and/or evacuating the reaction chamber. Onceagain, an oxygen source may be introduced into the reaction chamber toreact with the metal- or metalloid-containing precursor. Excess oxygensource is removed from the reaction chamber by purging and/or evacuatingthe reaction chamber. If a desired film thickness has been achieved, theprocess may be terminated. However, if a thicker film is desired, theentire four-step process may be repeated. By alternating the provisionof the Si-containing film forming composition, metal- ormetalloid-containing precursor, and oxygen source, a film of desiredcomposition and thickness can be deposited.

Additionally, by varying the number of pulses, films having a desiredstoichiometric M:Si ratio may be obtained. For example, a SiMO₂ film maybe obtained by having one pulse of the Si-containing film formingcomposition and one pulse of the metal- or metalloid-containingprecursor, with each pulse being followed by a pulse of the oxygensource. However, one of ordinary skill in the art will recognize thatthe number of pulses required to obtain the desired film may not beidentical to the stoichiometric ratio of the resulting film.

The silicon-containing films resulting from the processes discussedabove may include SiO₂; SiC; SiN; SiON; SiOC; SiONC; SiBN; SiBCN; SiCN;SiMO, SiMN in which M is selected from Zr, Hf, Ti, Nb, V, Ta, Al, Ge,depending of course on the oxidation state of M. One of ordinary skillin the art will recognize that by judicial selection of the appropriateSi-containing film forming composition and co-reactants, the desiredfilm composition may be obtained.

Upon obtaining a desired film thickness, the film may be subject tofurther processing, such as thermal annealing, furnace-annealing, rapidthermal annealing, UV or e-beam curing, and/or plasma gas exposure.Those skilled in the art recognize the systems and methods utilized toperform these additional processing steps. For example, thesilicon-containing film may be exposed to a temperature ranging fromapproximately 200° C. and approximately 1000° C. for a time ranging fromapproximately 0.1 second to approximately 7200 seconds under an inertatmosphere, a H-containing atmosphere, a N-containing atmosphere, orcombinations thereof. Most preferably, the temperature is 600° C. forless than 3600 seconds. Even more preferably, the temperature is lessthan 400° C. The annealing step may be performed in the same reactionchamber in which the deposition process is performed. Alternatively, thesubstrate may be removed from the reaction chamber, with theannealing/flash annealing process being performed in a separateapparatus. Any of the above post-treatment methods, but especiallyUV-curing, has been found effective to enhance the connectivity andcross linking of the film, and to reduce the H content of the film whenthe film is a SiN containing film. Typically, a combination of thermalannealing to <400° C. (preferably about 100° C.−300° C.) and UV curingis used to obtain the film with the highest density.

EXAMPLES

The following non-limiting examples are provided to further illustrateembodiments of the invention. However, the examples are not intended tobe all inclusive and are not intended to limit the scope of theinventions described herein.

Example 1

A 250 mL, 3-neck (24/40) European style flask with PTFE-coated magneticstir bar was charged with 9.56 g (33.7 mmol) anhydrous lithium iodidepowder (Sigma Aldrich, 99+%) and 80 mL anhydrous chloroform.Dichlorosilane (8.4 g; 83.2 mmol, excess)(“DCS”) was added to thereaction flask through the headspace while the mixture was stirred. Animmediate color change was observed (light purple coloration). Thetemperature rose from ˜22 to 29° C. during DCS exposure. The mixture wasstirred for an additional 18 hours at ambient temperature. The solidschanged in appearance from a coarse morphology with beige coloration towhite, finely divided powder. The mass of the solids decreased over thistime. The solids were filtered and dried under vacuum (2.75 g collected;3.0 g calculated). The solvent was removed under static vacuum bycondensation into a trap cooled in liquid nitrogen. The remaining purpleliquid was weighed (4.54 g; 10.0 g calculated; 45%) and analyzed by GCMS(80.5% SiH₂I₂ (“DIS”), remaining balance were higher boiling compounds).While the calculated product yield was unreliable due to sample size andthe means in which chloroform was removed, this example demonstratessuccessful halide exchange to produce the DIS product.

Example 2

A similar reaction was done using the same setup and reagent loadexplained in Example 1 except that toluene was used instead ofchloroform. GC sample analysis of the liquid (no further workup)revealed that DIS was the main product (sans solvent) with some DCS, andClSiH₂I.

Example 3

A 60 cc stainless steel ampule with diaphragm valve and pressure gaugewas charged with 4.25 g (31.7 mmol) anhydrous lithium iodide in anitrogen purged glove box. The nitrogen gas was removed under vacuum andDCS (1.60 g, 15.9 mmol) added by condensation (−196° C.). The containerwas then closed and allowed to thaw to ambient temperature and let standfor 30 minutes. Toluene extraction was performed. The toluene extractswere analyzed by GCMS, which revealed DCS, ClSiH₂I intermediate and DIS(main product). This example demonstrates that the process may becompleted without the use of a solvent.

Example 4

Sodium iodide powder (10.61 g; granular, colorless, crystalline solid)was exposed under static vacuum to excess DCS gas in a 50 cc Schlenktube with no visual indication of a reaction. No pressure change wasobserved. The DCS was then condensed into the Schlenk tube and thawed toambient temperature several times with no indication of reagent volumeloss, color or pressure change (no reaction). Reactions with sodiumiodide would likely require a solvent in which it has some solubility(i.e. methylene chloride, chloroform, acetonitrile, etc.). Lithiumiodide is clearly more reactive and preferable. This exampledemonstrates that the NaI alkali metal halide reactant is not asreactive as LiI.

Example 5

530 g product scale in pentane solvent: A 2 L, 3-neck round bottom (RB)flask with PTFE coated stir bar was charged with 500 g anhydrous LiI(solid)(3.74 mol; Acros Organics, 99%) and filled with anhydrousn-pentane (liquid) to the 1 L mark. The majority of the headspacenitrogen was removed in vacuo (to approximately 600 torr pressure) andan excess of DCS (liquid)(492 g; 4.87 mol; 2.8×mol excess) was added tothe flask through the headspace. The flask was periodically cooled to5-8° C. to allow full transfer. No stirring was achieved by using a stirplate/stir bar since the LiI solids were too heavy. The mixture wasagitated by frequently shaking/swirling the pot manually. The flask wasleft overnight at room temperature with the magnetic stirrer left on. Nostirring was achieved. The solids were filtered and dried under vacuum(169 g recovered; 158 g calculated). The light pink filtrate wasdistilled to remove pentane (b.p.=36° C.). The remaining colorlessliquid was distilled under reduced pressure (ca. 0-5 torr/21-31° C.)with the receiver cooled in dry ice pellets. This resulted in acolorless, frozen solid in the collector with almost no residual liquidleft behind in the distillation pot. The solid product was thawed andweighed (350 g; 530 g calculated; 65%). Gas Chromatographic/MassSpectrometric analysis revealed 91% (area percent) pure DIS with smallamounts of DCS (0.964%), pentane (0.326%), ClSiH₂I (4.953%) andimpurities tentatively assigned as perchlorinated/periodinateddisiloxane compounds (see FIG. 6).

The likely presence of siloxane-type impurities found in Example 5indicate that these compounds are formed by moisture derived from one ormore of the following:

-   -   Surface moisture from the glass reactor/distillation system        (unlikely).    -   From an air leak into the system.    -   Moisture in the lithium iodide starting material (reasonable        likelihood). This may also include some level of lithium        hydroxide.    -   Moisture from un-optimized sample preparation and handling for        GC analysis (entirely possible).

This highlights the importance of scrupulous measure to eliminate anypotential source of moisture throughout the process. Nevertheless, thesesiloxane impurities seem readily separable from the main product basedon their GC elution times.

Example 6

530 g product scale in pentane solvent: A 2 L, 3-neck RB flask withmechanical agitator, cooling cup condenser and ¼″ PTFE sparge tube wascharged with 500 g anhydrous LiI (3.74 mol; Acros Organics, 99%) andfilled with anhydrous n-pentane to the 1 L mark. Dichlorosilane (183 g;1.81 mol) was added subsurface over the course of 22 minutes in whichthe temperature rose from 18.1 (cold pentane) to 31.0° C. The reactionmixture was stirred vigorously and some reflux was observed during theaddition of DCS. The reaction mixture was stirred at ambient temperaturefor 3 hours and the liquid analyzed by GCMS. The chromatography revealedtrace DCS, pentane, ClSiH₂I partially substituted intermediate and DIS.The area percent of ClSiH₂I and DIS was 6 and 13.5%, respectively. Thereaction mixture was stirred an additional 18 hours. The solids werethen filtered and dried under vacuum (226 g collected, 158 gcalculated). The solvent and lower boiling impurities were removed bydistillation. Crude DIS (320 g, 89% by GC) was obtained (˜62%). Acomparison of Examples 5 and 6 demonstrate that varying thestoichiometric ratios of the reactants produces similar yields.

Example 7

500 g of LiI (3.74 moles; 99.9% City Chemical, colorless powder) wascharged into a 2 L, 3 neck RB flask with mechanical agitator. A coolingcup condenser and internal thermocouple were attached to the reactionapparatus. Approximately 800 mL anhydrous chloroform was added to theLiI powder. The condenser was cooled to −78° C. and 196 g dichlorosilane(1.94 mol, 3.5 mol % excess) under reduced pressure through thecondenser (−78° C. dry ice, isopropyl alcohol slush bath) in 15 minuteswith stirring. The pressure was 680 torr at 23° C. Additional nitrogengas was added to the reactor to a pressure of 780 torr. The mixture wasstirred for 22 hours upon which it took on a pink-purple coloration. Thesolids were filtered and dried under vacuum. The filtrate was collectedin a 1 L flask. The chloroform was distilled at 61° C. and the remainingpurple liquid collected and weighed (148 g, 28%, crude DIS product postsolvent removal). The low yield suggests that pure LiI has limited tolow solubility in chloroform. Some level of hydrogenation of the LiIreactant may facilitate reactivity of the salt and promote formation ofthe product, along with higher siloxane-based impurities.

Example 8

A four neck round bottom flask equipped with a mechanical stirrer, athermocouple and a dry-ice IPA condenser was charged with LiI (24.8 g,0.19 mol) under a stream of nitrogen. Pentane (80 mL) was transferredvia cannula. To the resulting mixture, TSA-Cl ((SiH₃)₂N(SiH₂Cl) 25 g,0.18 mol) was added dropwise over a period of 15 min at roomtemperature. No exothermicity was observed. After stirring for about 90min at ambient temperature, the reaction mixture was analyzed by GC-MSwhich shows 57% unreacted TSA-Cl and 39% TSA-I ((SiH₃)₂N(SiH₂I)) (FIG.7). At this point, the reaction mixture was allowed to stir overnight atroom temperature. The GC analysis after overnight stirring resulted in amajor peak corresponding to SiH₃—I and the peaks corresponding to TSA-Cland TSA-I disappeared. Optimization of the reaction time remainsongoing.

Example 9: Comparison of LI Particle Size

0.5-1 mm LiI

A 20 L jacketed filter reactor equipped with a mechanical stirrer,condenser (regulated to −70° C.), a solid addition port, an inlet tubefor sub-surface dichlorosilane addition and an inlet for liquid pentaneaddition was charged with pentane 15 L. The temperature in the reactorjacket was regulated to +35° C. and the reactor condenser regulated to−70° C. The reactor was then stirred ˜200 RPM and while under anatmosphere of Nitrogen, Lithium Iodide (12.25 kg, 91.52 mol) was thencharged to the reactor. Subsequent gravimetric addition ofdichlorosilane (4.52 kg, 44.75 mol) was regulated at a rate ofapproximately 1 kg per hour. Following completion of DCS addition, thereactor jacket remains regulated to +35° C. and the condenser to −70° C.After stirring for 16 hours, stirring was stopped and the reactorcontents were drained through the reactor filter into a 22 L roundbottomed flask. The salts on the reactor filter were then washed withpentane (3×1 L) to furnish 7.19 kg of solid residue. The combinedfiltrate and washings were subsequently distilled at 88 kPa to furnishcrude diiodosilane (9.04 kg, 83% purity). The remainder of the materialcomprised DCS, 1.3%; pentane, 0.6%; SiH₂ClI, 14.1% and SiHI₃, 0.1% assuggested by GC analysis. This crude material is further distilled at3.2 kPa to furnish diiodosilane (7.39 kg, 58% yield), comprising DIS,99.6%; SiH₃I, 0.1%; SiH₂ClI, 0.1%; SiHI₃, 0.15%, others, 0.12% assuggested by GC analysis. As discussed above, none of these impuritiescontain any carbon that could negatively affect the resultingSi-containing film.

1-1.25 mm LiI

A 20 L jacketed filter reactor equipped with a mechanical stirrer,condenser (regulated to −70° C.), a solid addition port, an inlet tubefor sub-surface dichlorosilane addition and an inlet for liquid pentaneaddition was charged with 15 L fresh pentane (Sigma Aldrich, >99%purity). The temperature in the reactor jacket was regulated to +35° C.and the reactor condenser regulated to −70° C. The reactor was thenstirred 200 RPM and while under an atmosphere of Nitrogen, LithiumIodide (9.99 kg, 74.64 mol) was then charged to the reactor. Subsequentgravimetric addition of dichlorosilane (3.88 kg, 38.42 mol) wasregulated at a rate of approximately 1 kg per hour. Following completionof DCS addition, the reactor jacket remains regulated to +35° C. and thecondenser to −70° C. After stirring for 16 hours, stirring was stoppedand the reactor contents were drained through the reactor filter into a22 L round bottomed flask. The salts on the reactor filter were thenwashed with pentane (3×1 L) to furnish 4.96 kg of solid residue. Thecombined filtrate and washings were subsequently distilled at 88 kPa tofurnish crude diiodosilane (8.01 kg, 86% purity). The remainder of thematerial comprised DCS, 0.1%, pentane, 1.2%; SiH₃I, 0.1%, SiH₂ClI, 4.5%and SiHI₃, 0.1% as suggested by GC analysis. This crude material isfurther distilled at 3.2 kPa to furnish diiodosilane (8.16 kg, 77%yield), comprising DIS, 99.7%; SiH₃I, 0.01%; SiH₂ClI, 0.03% and SiHI₃,0.1%. As discussed above, none of these impurities contain any carbonthat could negatively affect the resulting Si-containing film.

These results also show that the particle size of Lithium Iodideinfluences the isolated yield. Surprisingly, improved yields areobserved when a larger particle size of Lithium Iodide is employedrelative to a smaller particle size.

Example 10: Effect of Solvent Recycling

Solvent Recycling

A 20 L jacketed filter reactor equipped with a mechanical stirrer,condenser (regulated to −70° C.), a solid addition port, an inlet tubefor sub-surface dichlorosilane addition and an inlet for liquid pentaneaddition was charged with 15 L pentane. The temperature in the reactorjacket was regulated to +35° C. and the reactor condenser regulated to−70° C. The reactor was then stirred ˜200 RPM and while under anatmosphere of Nitrogen, Lithium Iodide (12.34 kg, 92.19 mol) was thencharged to the reactor. Subsequent gravimetric addition ofdichlorosilane (4.25 kg, 42.08 mol) was regulated at a rate ofapproximately 1 kg per hour. Following completion of DCS addition, thereactor jacket remains regulated to +35° C. and the condenser to −70° C.After 16 hours stirring, stirring was stopped and the reactor contentswere drained through the reactor filter into a 22 L round bottomedflask. The salts on the reactor filter were then washed with pentane(3×1 L). The combined filtrate and washings were subsequently distilledat 88 kPa to furnish crude diiodosilane (9.26 kg, 82% purity) in thedistillation pot. The distillate (11 L, comprising mostly of pentane,82%; DCS, 12%; SiH₂ClI, 4% and DIS, 1%) was recycled back to the reactorfor a consecutive synthesis.

Accordingly, the aforementioned 20 L jacketed filter reactor equippedwith a mechanical stirrer, condenser (regulated to −70° C.), solidaddition port, inlet tube for sub-surface dichlorosilane addition and aninlet for distillate/pentane addition was charged with the recycleddistillate (11 L, comprising mostly of pentane, 82%; DCS, 12%; SiH₂ClI,4% and DIS, 1%) from the previous production run together with freshpentane (4 L). The temperature in the reactor jacket was regulated to+35° C. and the reactor condenser regulated to −70° C. The reactor wasthen stirred ˜200 RPM and while under an atmosphere of Nitrogen, LithiumIodide (12.38 kg, 92.49 mol) was then charged to the reactor. Subsequentgravimetric addition of dichlorosilane (4.17 kg, 41.28 mol) wasregulated at a rate of approximately 1 kg per hour. Following completionof DCS addition, the reactor jacket remains regulated to +35° C. and thecondenser to −70° C. After 17 hours stirring, stirring was stopped andthe reactor contents were drained through the reactor filter into a 22 Lround bottomed flask. The salts on the reactor filter were then washedwith pentane (3×1 L). The combined filtrate and washings weresubsequently distilled at 88 kPa to furnish crude diiodosilane (8.77 kg,84% purity) as distillation bottoms in the distillation pot. This crudematerial is further distilled at 3.2 kPa to furnish diiodosilane (7.29kg, 62% yield), comprising DIS, 99.5%; SiH₃I, 0.14%; SiHI₃, 0.24%,others, 0.12%.

Fresh Solvent

A 20 L jacketed filter reactor equipped with a mechanical stirrer,condenser (regulated to −70° C.), a solid addition port, an inlet tubefor sub-surface dichlorosilane addition and an inlet for liquid pentaneaddition was charged with 15 L fresh pentane (Sigma Aldrich, >99%purity). The temperature in the reactor jacket was regulated to +35° C.and the reactor condenser regulated to −70° C. The reactor was thenstirred ˜200 RPM and while under an atmosphere of Nitrogen, LithiumIodide (12.47 kg, 93.16 mol) was then charged to the reactor. Subsequentgravimetric addition of dichlorosilane (4.85 kg, 48.02 mol) wasregulated at a rate of approximately 1 kg per hour. Following completionof DCS addition, the reactor jacket remains regulated to +35° C. and thecondenser to −70° C. After stirring for 16 hours, stirring was stoppedand the reactor contents were drained through the reactor filter into a22 L round bottomed flask. The salts on the reactor filter were thenwashed with pentane (3×1 L). The combined filtrate and washings weresubsequently distilled at 88 kPa to furnish crude diiodosilane (8.01 kg,86% purity). This crude material is further distilled at 3.2 kPa tofurnish diiodosilane (6.68 kg, 51% yield), comprising DIS, 99.9%; SiH₃I,0.01% and SiHI₃, 0.02%.

As can be seen, recycling offers advantages in terms of economic andenvironmental benefits along with often simplifying regulatorycompliance, however, impurities may accumulate. Eliminating therecycling step and using a fresh solvent charge for each synthetic runleads to an ultra-high product purity level that is not attainable aftersolvent recycling.

Example 11: Material Compatibility

Small pieces of material were submerged in SiH₂I₂ (synthesized permethod disclosed in US Pat App Pub No 2016/0264426), sealed in a glasspressure tube and maintained in the absence of light at the statedtemperature for the stated time period. The initial control assay was96.9% SiH₂I₂ with 1.3% SiH(Me)I₂ and 1.6% SiHI₃, based on GCMS peakintegration. The results are provided below and demonstrate that thestability of SiH₂I₂ is difficult to maintain. Applicants believe thatthe HX or X₂ reactants used in that synthesis method contribute to theinstability of the SiH₂I₂ reaction product demonstrated in the Controlresults below. As can be seen, some standard packaging materials furtheraccelerate decomposition of the SiH₂I₂ product.

Room Temperature:

Material 3 weeks 8 weeks 12 weeks Control* 96.9% SiH₂I₂ 96.1% SiH₂I₂95.7% SiH₂I₂ 1.3% SiH(Me)I₂ 1.3% SiH(Me)I₂ 1.3% SiH(Me)I₂ 1.6% SiHI₃2.4% SiHI₃ 2.8% SiHI₃ Stainless Steel 94.4% SiH₂I₂ 92.4% SiH₂I₂ 94.7%SiH₂I₂ (SUS316) 1.8% SiH(Me)I₂ 1.6% SiH(Me)I₂ 1.3% SiH(Me)I₂ 3.5% SiHI₃5.6% SiHI₃ 5.8% SiHI₃ 0.1% SiI₄ Aluminum 97.8% SiH₂I₂ 97.3% SiH₂I₂ 97.3%SiH₂I₂ Oxide 0.9% SiH(Me)I₂ 0.9% SiH(Me)I₂ 0.8% SiH(Me)I₂ (Sapphire)1.1% SiHI₃ 1.7% SiHI₃ 1.8% SiHI₃ Aluminum 0.2% SiHI₃ 0.5% SiHI₃ 0.6%SiHI₃ (A6061) 91.9% SiH₂I₂ 93.6% SiH₂I₂ 92.4% SiH₂I₂ 1.0% SiH(Me)I₂ 0.9%SiH(Me)I₂ 0.8% SiH(Me)I₂ 5.0% SiHI₃ 5.0% SiHI₃ 6.2% SiHI₃ 03% SiI₄Aluminum 0.2% SiHI₃ 0.8% SiHI₃ 1.1% SiHI₃ (4NGM) 92.0% SiH₂I₂ 89.6%SiH₂I₂ 87.4% SiH₂I₂ 1.1% SiH(Me)I₂ 0.9% SiH(Me)I₂ 0.9% SiH(Me)I₂ 5.9%SiHI₃ 8.1% SiHI₃ 10.0% SiHI₃ 0.2% SiI₄ 0.5% SiI₄ 0.4% SiI₄ Aluminum97.8% SiH₂I₂ 97.1% SiH₂I₂ 95.9% SiH₂I₂ Oxide (Al₂O₃) 0.9% SiH(Me)I₂ 0.8%SiH(Me)I₂ 0.8% SiH(Me)I₂ 1.1% SiHI₃ 1.9% SiHI₃ 3.2% SiHI₃ Aluminum 95.0%SiH₂I₂ 96.2% SiH₂I₂ 94.0% SiH₂I₂ nitride (AlN- 1.1% SIH(Me)I₂ 1.0%SiH(Me)I₂ 1.0% SiH(Me)I₂ ceramic) 3.6% SiHI₃ 2.6% SiHI₃ 4.8% SiHI₃*Different starting material: 97.6% SiH₂I₂, 0.9% SiH(Me)I₂, and 0.9%SiH₃.40° C.

Material 3 weeks 8 weeks 12 weeks Control* 95.8% SiH₂I₂ 94.4% SiH₂I₂92.8% SiH₂I₂ 1.0% SiH(Me)I₂ 1.1% SiH(Me)I₂ 1.0% SiH(Me)I₂ 2.9% SiHI₃4.2% SiHI₃ 6.1% SiHI₃ Stainless Steel 94.9% SiH₂I₂ 93.8% SiH₂I₂ 91.5%SiH₂I₂ (SUS316) 1.0% SiH(Me)I₂ 0.9% SiH(Me)I₂ 0.9% SiH(Me)I₂ 3.8% SiHI₃5.3% SiHI₃ 7.4% SiHI₃ Aluminum 92.9% SiH₂I₂ 86.8% SiH₂I₂ 0.1% SiHI₃Oxide 1.3% SiH(Me)I₂ 2.3% SiH(Me)I₂ 83.2% SiH₂I₂ (Sapphire) 5.3% SiHI₃10.6% SiHI₃ 1.9% SiH(Me)I₂ 14.5% SiHI₃ Aluminum 0.7% SiHI₃ 1.6% SiHI₃2.0% SiHI₃ (A6061) 88.6% SiH₂I₂ 83.6% SiH₂I₂ 78.8% SiH₂I₂ 0.8% SiH(Me)I₂0.6% SiH(Me)I₂ 0.5% SiH(Me)I₂ 9.3% SiHI₃ 13.7% SiHI₃ 18.4% SiHI₃ 0.1%SiI₄ 0.3% SiI₄ Aluminum 0.6% SiHI₃ 1.2% SiHI₃ 1.9% SiHI₃ (4NGM) 91.4%SiH₂I₂ 88.3% SiH₂I₂ 81.9% SiH₂I₂ 0.6% SiH(Me)I₂ 0.6% SiH(Me)I₂ 0.5%SiH(Me)I₂ 7.3% SiHI₃ 9.9% SiHI₃ 15.6% SiHI₃ Aluminum 96.9% SiH₂I₂ 95.8%SiH₂I₂ 94.0% SiH₂I₂ Oxide (Al₂O₃) 0.9% SiH(Me)I₂ 0.7% SiH(Me)I₂ 0.8%SiH(Me)I₂ 2.0% SiHI₃ 3.4% SiHI₃ 5.1% SiHI₃ Aluminum 96.1% SiH₂I₂ 91.0%SiH₂I₂ 89.4% SiH₂I₂ nitride (AlN- 0.8% SiH(Me)I₂ 0.8% SiH(Me)I₂ 0.8%SiH(Me)I₂ ceramic) 3.0% SiHI₃ 8.1% SiHI₃ 9.8% SiHI₃ *Different startingmaterial: 97.6% SiH₂I₂, 0.9% SiH(Me)I₂, and 0.9% SiH₃.

Example 11: Stability

SiH₂I₂ synthesized per the methods disclosed herein was stored at roomtemperature in passivated stainless steel cylinders. Assays wereperformed using GCMS peak integration prior to and after storage in thecylinders. The table below demonstrates that this product maintains itspurity without the need for any stabilizer.

Sample Initial Assay Post storage Assay Time Period 1 99.3% 99.1% 21days 2 99.8% 99.4%  3 months 3 99.7% 99.0% 40 days 4 99.7% 99.3% 40 days

Example 12 Dynamic Thermal Stability

Liquid and gas phase DIS samples were analyzed by gas chromatographyequipped with a thermal conductivity detector (GC-TCD) or GCMS over 282days under dynamic conditions that mimic the “vapor drawn mode” ofoperation that may be used in some atomic layer deposition processes.The “vapor drawn mode” is accomplished using a He inert gas in theSi-containing film forming composition delivery device similar to thatof FIGS. 3 and 4, with the ends of both the inlet and outlet locatedabove the surface of the Si-containing film forming composition. Thedevice initially contained 1 kg of DIS and was maintained at 35° C.during testing. The liquid phase DIS samples were taken from thedelivery device. The gas phase DIS samples were taken from a samplingport of a delivery line connected to the outlet port of the deliverydevice. The results are summarized in the table below:

Start ⅔ Usage Liquid Liquid ⅔ Usage >95% Usage >95% Usage Phase PhaseGas Phase Liquid Phase Gas Phase GC-TCD GC-TCD GC-MS GC-TCD GC-MS SiH₃I0.25% ND ND ND ND SiHI₃ 0.34%  2.6% ND 19.59% ND SiH₂I₂ 99.27%97.31% >99.9% 80.41% >99.9%

As shown above, despite some apparent disproportionation that occurs inthe liquid phase during depletion of the dispensing device asillustrated by the decrease in DIS composition at ⅔ and >95% usage, thepurity of the gas phase remains high and of semiconductor grade quality.Therefore, liquid DIS synthesized according to the methods disclosedherein delivers a stable composition of vapor phase DIS to the vapordeposition tool without the need for any stabilizer.

Prophetic Example: Synthesis of I₃Si—CH₂—SiI₃

Cl₃Si—CH₂—SiCl₃+6Li—I→I₃Si—CH₂—SiI₃+6Li—Cl

Under inert and anhydrous conditions, a flask will be charged withlithium iodide and pentane or other suitable solvent followed by slowaddition of a solution or solvent free liquidbis(trichlorosilyl)methane. The suspension will be stirred vigorouslyuntil the completion of the reaction is observed by disappearance ofbis(trichlorosilyl)methane in a GCMS trace of an aliquot of the reactionmixture. The resultant suspension will be filtered over a medium glassfrit loaded with a pad of diatomaceous earth to yield a pentane solutionof the desired product. The bis(triiodosilyl)methane product will beisolated in pure form by reduced pressure distillation and/orsublimation.

The reactants are commercially available or may be synthesized accordingto J. Organomet. Chem. 92, 1975 163-168.

While embodiments of this invention have been shown and described,modifications thereof may be made by one skilled in the art withoutdeparting from the spirit or teaching of this invention. The embodimentsdescribed herein are exemplary only and not limiting. Many variationsand modifications of the composition and method are possible and withinthe scope of the invention. Accordingly, the scope of protection is notlimited to the embodiments described herein, but is only limited by theclaims which follow, the scope of which shall include all equivalents ofthe subject matter of the claims.

What is claimed is:
 1. A method of synthesizing a Si—H containingiodosilane having the formula Si_(w)H_(x)I_(z) or N(SiH_(a)I_(c))₃,wherein w=1 to 3, x+z=2w+2, x=1 to 2w+1, z=1 to 2w+1, each a isindependently 0 to 3, each c is independently 0 to 3, a+c=3, providedthat at least one a is 1 and at least one c is 1, the method comprising:contacting a halosilane reactant having the formula Si_(w)H_(x)X_(z) orN(SiH_(a)X_(c))₃, wherein X is Cl or Br, and w, x, z, a, and c are asdefined above, with an alkali metal halide reactant having the formulaMI, wherein M is Li, Na, K, Rb, or Cs, to produce a combination of MXand Si_(w)H_(x)I_(z) or N(SiH_(a)I_(c))₃; and isolating the mixture toproduce the Si—H containing iodosilane having the formulaSi_(w)H_(x)I_(z) or N(SiH_(a)I_(c))₃.
 2. The method of claim 1, whereinthe halosilane reactant is SiH₂Cl₂.
 3. The method of claim 2, whereinthe alkali metal halide reactant is LiI.
 4. The method of claim 1,wherein the halosilane reactant is Si₂HCl₅.
 5. The method of claim 1,wherein the halosilane reactant is (SiH₃)₂N(SiH₂Cl).
 6. The method ofclaim 1, wherein the alkali metal halide reactant is LiI.